The Simplest Iminophosphane HPNH and Its Photoisomerization to Aminophosphinidene H2NP

The Simplest Iminophosphane HPNH and Its Photoisomerization to Aminophosphinidene H2NP | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article The Simplest Iminophosphane HPNH and Its Photoisomerization to Aminophosphinidene H 2 NP Xiaoqing Zeng, Junjie Jiang, Yixing Guo, Longtian Huang, Lina Wang, and 1 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7398545/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 22 Jan, 2026 Read the published version in Nature Communications → Version 1 posted You are reading this latest preprint version Abstract The simplest iminophosphane HPNH and aminophosphinidene H 2 NP are prototype molecules bearing phosphorus-nitrogen multiple bonds; however, both species remain hitherto unobserved. Here, we report the first time synthesis and characterization of HPNH and H 2 NP. Specifically, the cis and trans conformers of HPNH have been prepared in the gas phase by high-vacuum flash pyrolysis of di- tert -butylphosphanamine at ca. 950 K and subsequently isolated in solid N 2 -matrices at 10 K for the characterization by matrix-isolation IR (with D- and 15 N-isotope labeling) and UV-vis spectroscopy. In addition to the photo-induced conformational interconversion between trans -HPNH and cis -HPNH, their photoisomerization with H 2 NP has also been observed in the cryogenic matrices. In accordance with the very recently predicted lower energy of the singlet state than the triplet state by 0.2 kcal mol – 1 for H 2 NP, its experimental IR spectrum shows good agreement with the calculations for the singlet state at the CCSD(T)-F12B/VTZ-F12 level using configuration-selective vibrational configuration interaction (VCI) theory. Upon photoexciation at 395 nm, the matrix-isolated H 2 NP reacts with CO and O 2 to yield H 2 NPCO and H 2 NPO 2 as the trapping and oxidation products, respectively. Physical sciences/Chemistry/Inorganic chemistry/Chemical bonding Physical sciences/Chemistry/Physical chemistry/Chemical physics Figures Figure 1 Figure 2 Figure 3 Figure 4 Introduction The chemistry of multiply bonded compounds involving group 15 elements keeps attracting enormous interest, not only due to the novel structural and bonding properties but also their broad applications in synthetic chemistry and materials science. 1 – 3 Particularly, an extremely important role in the main group chemistry has been played by low-valent phosphorus. As a heavy analogue to molecular nitrogen (N 2 ), the diatomic phosphorus mononitride (PN) was first spectroscopically detected in the gas phase in 1933. 4 Chemically, PN is very reactive, and it aggregates spontaneously above 10 K to form polymeric (PN) n 5 , 6 and the Hückel aromatic cyclotriphosphazene P 3 N 3 . 7 , 8 As the first phosphorus-containing species detected in the interstellar medium, 9 , 10 PN plays a key role in the chemical network of phosphorus astrochemistry. 11 Quite recently, PN and another small phosphorus compound •PO were observed in the dense molecular cloud WB89-621 at the edge of the Galaxy. 12 , 13 Considering the essential role of the phosphorus element in the origin and evolution of life, the prebiotic chemistry of PN 11 , 14 – 16 and other astronomically detected P-bearing molecules such as •PO, 17 PH 3 , 18 and HCP 19 have been extensively explored. To explore the synthetic applications, stable compounds containing terminal PN unit have been synthesized and used as precursors for the release of PN under catalytic conditions. 20 – 24 As the simple derivatives of PN, the three isomers HPNH, H 2 NP, and H 2 PN serve as prototype molecules consisting of phosphorus-nitrogen multiple bonds. Particularly, HPNH is the simplest iminophosphane that has been proposed as a candidate interstellar species, which could be formed through hydrogenation of PN via intermediacy of the HPN• and HNP• radicals. 25 , 26 The structural and bonding properties of HPNH have been extensively explored 27 – 31 by quantum chemical calculations since the first theoretical study by Trinquier in 1982. 32 Theoretically, HPNH can exist in planar trans or cis conformations, and the former is slightly lower in energy by 1 kcal mol – 1 (Scheme 1 ). Moreover, trans- HPNH ( trans - 1 , Scheme 1 ) is the global minimum on the potential energy surface of the [2H, P, N] system, and its thermal stability is secured with the large barriers (> 60 kcal mol – 1 ) for its isomerization to the two less stable isomers H 2 NP ( 3 ) and H 2 PN ( 2 ) via 1,2-hydrogen migration. However, all the early attempts to generate HPNH were unsuccessful, 33 whereas, a number of the sterically protected and the carbene-stabilized iminophosphanes has been synthesized and broadly used in organophosphorus chemistry. 34 – 40 Among the [2H, P, N] isomers, the least stable isomer H 2 PN features as the parent phosphinonitrene, and it was calculated to have closed-shell singlet ground state ( singlet - 2 ) due to electron delocalization of the lone pair electrons, leading to a strongly polarized shorter PN double bond than those in HPNH. In contrast, the triplet state ( triplet - 2 ) is less stable by 16.7 kcal mol – 1 . Experimentally, H 2 PN has so far resisted all attempts at its detection including the recent attempted generation from photodecomposition of H 2 PNCO. 25 Notably, singlet phosphinonitrenes stabilized by sterically demanding substituents have been synthesized 41 – 43 and used for the activation of small molecules. 44 In contrast to the large singlet-triplet energy gap for H 2 PN, the ground-state spin multiplicity of the isomeric H 2 NP remains unclear as the sign for the predicted singlet-triplet energy gap depends on the theoretical methods. 28 , 32 , 45 According to the most recent calculations by Schaefer III et al., 46 the singlet state is slightly lower by 0.2 kcal mol – 1 due to effective electron delocalization of the lone pair electrons in the singlet state ( singlet - 3 ), and it contains an ideal phosphorus-nitrogen double bond with a bond order of 2, whereas, triplet - 3 features a smaller bond order of 1.5. Similar to the elusiveness of HPNH and H 2 PN, recent attempts to generate H 2 NP from photodecomposition of H 2 NPCO in cryogenic matrix 47 and thermal decomposition of a dibenzo-7-phosphanorbornadiene precursor in the gas phase 48 were unsuccessful. This is in sharp contrast to the analogous systems H 2 PP/HPPH 49 and H 2 NN/HNNH, 50 which have already been well characterized. Herein, we report the first time preparation and characterization of cis- HPNH, trans- HPNH, and H 2 NP in cryogenic matrices at 10 K. In addition to the photo-induced interconversion among these isomers, the photoreactions of H 2 NP with CO and O 2 have also been studied. Results and Discussion Generation and characterization of HPNH The preparation of HPNH was performed by high-vacuum flash pyrolysis (HVFP) of di- tert -butylphosphanamine (( t -Bu) 2 PNH 2 ) in the gas phase at ca. 950 K (Scheme 2 ). A typical IR spectrum for the thermolysis products isolated in a solid N 2 -matrix at 10 K (Fig. 1 A) shows IR bands of the fragments C 4 H 8 and C 4 H 10 , 51 along with some weak bands of the counterpart fragment HPNH. When using the deuterated precursor ( t -Bu) 2 PND 2 , the mono-deuterated dissociation products HPND and [D 1 ]-C 4 H 10 were identified (Fig. S2), implying that the dissociation of ( t -Bu) 2 PNH 2 likely proceeds in a stepwise pathway (Scheme 2 ). Considering the TD-DSD-PBEP86/aug-cc-pVTZ calculated absorption at 432 nm for the π* ← n transition in trans -HPNH (Table S1 ), the matrix containing the pyrolysis products of ( t -Bu) 2 PNH 2 was subjected to the irradiation at 410 nm. The resulting IR difference spectrum (Fig. 1 B) reflecting the changes of the matrix shows selective depletion of trans -HPNH with a group of IR bands at 3309.1, 2225.0, 1107.0, 1012.8, 953.5, and 911.0 cm – 1 along with the concomitant appearance of another group of IR bands at 3334.2, 2135.2, 1074.8, 1023.5, 897.4, and 816.9 cm – 1 for cis -HPNH. Notably, the IR bands for cis -HPNH are also detectable in the spectrum of the decomposition products of the precursor, indicating that both conformers of HPNH were produced in the gas phase. To aid the identification, quantum chemical calculations on the IR spectra for the two conformers of HPNH (Table 1 ) were carried out at the CCSD(T)-F12B/VTZ-F12 level of theory using configuration-selective vibrational configuration interaction theory (VCI). 52 Additionally, isotope labeling experiment was performed by using ( t -Bu) 2 P 15 NH 2 as the precursor to HP 15 NH (Figs. S1 and S5). Table 1 Calculated and observed IR data for the two conformers of HPNH. cis- HPNH trans- HPNH mode [e] ν Δν(H/D) [c] Δν( 14/15 N) [d] ν Δν(H/D) Δν( 14/15 N) Cal. [a] Obs. [b] Cal. Obs. Cal. Obs. Cal. Obs. Cal. Obs. Cal. Obs. 3345.5 (7) 3334.2 (39) −862.3 −863.7 −7.4 −7.4 3299.5 (8) 3309.1 (40) −851.2 −844.3 −6.6 −7.1 ν 1 , ν(NH) 2120.3 (147) 2135.3 (100) −3.1 −0.2 0 0 2212.9 (123) 2225.0 (100) + 0.4 + 0.5 0 0 ν 2 , ν(PH) 1022.4 (31) 1023.5 (47) −31.0 −29.2 −13.2 −12.1 1096.8 (23) 1107.0 (33) −42.4 −37.0 −8.4 −8.5 ν 3 , δ(NH) 1073.2 (5) 1074.8 (7) −36.5 −33.8 −11.7 −11.8 1005.7 (50) 1012.8 (89) −13.6 −8.2 −18.2 −18.9 ν 4 , ν(PN) 897.0 (68) 897.4 (83) −150.3 −148.8 −2.8 −2.9 951.6 (27) 953.5 (43) −164.5 −160.0 −1.7 −1.8 ν 6 , δ(HPNH) 807.4 (84) 816.9 (87) −171.7 −173.6 −2.3 −2.0 895.0 (40) 911.0 (80) −198.4 −204.6 −0.6 −0.7 ν 5 , δ(HPNH) [a] Calculated IR frequencies and intensities (km mol – 1 , in parentheses) at the CCSD(T)-F12B/VTZ-F12 level of theory using configuration-selective vibrational configuration interaction theory (VCI). [b] Observed band position (cm – 1 ) for the strongest matrix site in N 2 -matrix at 10 K. [c] Calculated and observed D-isotopic shifts for HPND. [d] Calculated and observed 15 N-isotopic shifts for HP 15 NH. [e] Assignment of the vibrational modes. In the IR spectrum of trans -HPNH, the band at 3309.1 cm – 1 shows D- and 15 N-isotopic shifts of − 844.3 and − 7.1 cm – 1 , respectively, supporting its assignment to the NH stretching mode with a calculated frequency of 3299.5 cm – 1 . The frequency is lower than that in cis -HPNH (obs. 3334.2 cm – 1 ; cal. 3345.5 cm – 1 ), for which the D- and 15 N-isotopic shifts are − 863.7 and − 7.4 cm – 1 , respectively. The NH stretching frequencies in the two conformers of HPNH are close to the same mode in HNSO (3308.5 cm – 1 ). 53 , 54 The frequency for the PH stretching mode in trans -HPNH (obs. 2225.0 cm – 1 ; cal. 2212.9 cm – 1 ) is significantly higher than that in cis -HPNH (obs. 2135.0 cm – 1 ; cal. 2120.3 cm – 1 ), whereas, both are lower than the same mode in HPCO (2311.8 cm – 1 ) 55 , 56 and HPNN (2322.1 cm – 1 ). 57 , 58 The band at 1012.8 cm – 1 with a large 15 N-isotopic shift of − 18.9 cm – 1 for trans -HPNH mainly involves the PN stretching vibration, and it couples with the NH bending at 1107.0 cm – 1 as evidenced by the 15 N-isotopic shift of − 8.5 cm – 1 . This vibrational coupling becomes more evident in the cis conformer due to the nearly equivalent 15 N-isotopic shifts of − 11.8 and − 12.1 cm – 1 for the two bands at 1074.8 and 1023.5 cm – 1 , respectively. The PN stretching frequencies in the two conformers of HPNH are lower than those in FPNF (1116.8 cm – 1 , Δν( 14/15 N) = − 25.3 cm – 1 ) 59 and HNP• (1136.3 cm – 1 , Δν( 14/15 N) = − 22.7 cm – 1 ). 25 The last two bands for HPNH belong to the out-of-plane and in-plane deformation modes of the PH and NH moieties, respectively. Additionally, two very weak bands at 2207.6 and 2086.5 cm – 1 show similar changes with the other bands of trans -HPNH and cis -HPNH, respectively, and they belong to the ν 3 overtone of trans -HPNH and the ν 3 + ν 4 combination of cis -HPNH according to the corresponding D- and 15 N-isotopic shifts, as well as the theoretically predicted anharmonic frequencies of 2198.0 and 2083.0 cm – 1 , respectively. In line with the calculated absorption at 376 nm for cis -HPNH (Table S1 ), the reverse cis to trans conformational transformation in HPNH was observed upon subsequent photoexcitation at 365 nm (Fig. 1 C). Consistent with the trans -HPNH → cis -HPNH photoisomerization observed by matrix-isolation IR spectroscopy, a weak absorption at around 420 nm in the UV-vis spectrum of the matrix-isolated HVFP products of ( t -Bu) 2 PNH 2 was depleted by the irradiation at 410 nm, leading to the concomitant increase of another very weak absorption at around 340 nm (Fig. 2 A). The assignment of the visible absorption (ca. 420 nm) to trans -HPNH is supported by the good agreement with the calculated transition at 432 nm (Table S1 ) for the excitation of the phosphorus lone-pair electron to the anti-bonding π* orbital. The UV-absorption (ca. 340 nm) corresponds to the similar transition of the cis conformer with a calculated band at 376 nm. Photoisomerization of HPNH to HNP In addition to the photo-induced conformational rotation in HPNH, further photoexcitation of HPNH at 395 nm promotes 1,2-H migration to yield H 2 NP with IR bands at 3386.3, 3313.4, 947.6, 943.2, and 739.8 cm – 1 (Fig. 2 B). Accordingly, the absorptions for HPNH ( cis and trans ) decrease in the UV-vis spectrum (Fig. 2 A). Consequently, new absorptions at 290 and 240 nm for the isomer H 2 NP appear (Fig. 2 A), and they are in good agreement with the calculated vertical transitions at 302 and 232 nm for H 2 NP in the singlet state (Table S1 ). Consistent with the observed absorption at 290 nm for H 2 NP, subsequent irradiation of the matrix at 310 nm causes reformation HPNH from H 2 NP (Fig. 2 C). The photolytic interconversion between HPNH ( cis and trans ) and H 2 NP under the matrix-isolation conditions enables unambiguous identification of the weak IR bands for H 2 NP. The two bands at 3386.3 and 3313.4 cm – 1 with D-isotopic shifts of − 33.1 and − 829.9 cm – 1 in H(D)NP are reasonably assigned to the NH 2 stretching modes, and they show better agreement with the VCI calculated values for H 2 NP in the singlet state (3379.9 and 3322.2 cm – 1 ) than those in the triplet state (3493.1 and 3423.9 cm – 1 , Table 2 ). In accordance with the VCI calculated frequencies of 951.6 and 949.4 cm – 1 for the NH 2 deformation and NP stretching modes in singlet H 2 NP, two bands at 947.6 and 943.2 cm – 1 are observable in the IR difference spectrum (Fig. 2 C). However, the VCI calculated frequencies for the same modes in triplet H 2 NP (845.6 and 813.9 cm – 1 ) differ from the singlet state by more than 100 cm – 1 . Additionally, the NH 2 wagging mode locates at 739.8 cm – 1 (cal. 723.0 cm – 1 ) as a broad band, and it shows a large D-isotopic shift of − 74.5 cm – 1 (cal. −74.5 cm – 1 ) in H(D)NP. Table 2 Calculated and observed IR data for H 2 NP. ν Δν(H/D) [c] Δν( 14/15 N) [d] mode [e] triplet [a] singlet [a] Obs. [b] Cal. Obs. Cal. Obs. 3493.1 (37) 3379.9 (33) 3386.3 (27) −30.9 −33.1 −9.8 −9.4 ν 1 , ν as (NH 2 ) 3423.9 (25) 3322.2 (< 1) 3313.4 (1) −838.7 −829.9 −4.8 −6.0 ν 2 , ν s (NH 2 ) 1558.3 (20) 1608.2 (2) n.o. [f] −167.4 n.o. −5.7 n.o. ν 3 , δ(NH 2 ) 845.6 (76) 951.6 (33) 947.6 (6) −3.1 n.o. −18.2 n.o. ν 4 , ν(NP) 813.9 (2) 949.4 (17) 943.2 (4) −170.1 −157.9 −4.0 −2.5 ν 5 , ρ(NH 2 ) 170.3 (110) 723.0 (177) 739.8 (100) −74.5 −74.5 −4.7 −3.8 ν 6 , ω(NH 2 ) [a] Calculated IR frequencies (> 400 cm – 1 ) and intensities (km mol – 1 , in parentheses) at the CCSD(T)-F12B/VTZ-F12 level of theory using configuration-selective vibrational configuration interaction theory (VCI) for H 2 NP. [b] Observed band position (cm – 1 ) for the strongest matrix site in N 2 -matrix at 10 K. [c] Calculated and observed D-isotopic shifts for singlet H(D)NP. [d] Calculated and observed 15 N-isotopic shifts for singlet H 2 15 NP. [e] Assignment of the vibrational modes. [f] Not observed due to overlap with the IR band of H 2 O. Photoreactions of HNP In an attempt to generate the least stable isomer H 2 PN on the potential energy surface of the [2H, N, P] system, photoexcitation of the matrix-isolated HPNH was carried out by using short-wavelength irradiations at 254 and 193 nm. However, no isomerization but dehydrogenation to yield PN was observed. Additionally, chemical trapping reaction was performed by photolysis of HPNH at 395 nm in solid CO ice at 10 K. The corresponding IR difference spectrum (Fig. 3 A) shows exclusive formation of H 2 NPCO, 47 implying first formation of H 2 NP from HPNH with subsequent reaction by CO. Similar photolytic CO-trapping reactions were observed before for singlet phosphinophosphinidenes 60 and triplet phenylphosphinidene. 61 , 62 Absence of the CO-trapping product of the putative intermediate H 2 PN (+ CO → H 2 PNCO) suggests that it is not involved in the photochemistry of HPNH, since similar CO-trapping reaction was observed before for the fluorine derivative F 2 PN (+ CO → F 2 PNCO). 59 To further explore the reactivity of H 2 NP, its oxidation by molecular oxygen was studied in an O 2 -doped N 2 -matrix (5%) at 10 K. Upon 395 nm irradiation, a new species forms with a group of IR bands at 3529.6, 3423.4, 1540.0, 1434.7, 1191.7, and 909.8 cm – 1 (Fig. 3 B). The two bands at 1434.7 and 1191.7 cm – 1 exhibit large 18 O-isotopic shifts of − 40.2 and − 37.6 cm – 1 , supporting their assignment to the asymmetric and symmetric OPO stretching vibration modes in the oxidation product H 2 NPO 2 (← H 2 NP + O 2 ). The two stretching modes are close to the same modes in other dioxophosphoranes CH 3 PO 2 (1404.3 and 1159.6 cm – 1 , N 2 -matrix) 63 and PhPO 2 (1416 and 1170 cm – 1 , Ar-matrix). 61 The three bands at 3529.6, 3423.4, and 1540.0 cm – 1 correspond to the stretching and deformation of the NH 2 moiety, and they resemble the same modes in the nitrogen analogue NH 2 NO 2 (3478.0, 3359.3, and 1558.1 cm – 1 , Ar-matrix). 64 , 65 The identification of H 2 NPO 2 is further supported by the good agreement of the observed IR spectrum with the theoretical calculations (3550.4, 3439.7, 1531.3, 1417.7, and 1160.7 cm – 1 , Table S2). Considering the previously observed spontaneous O 2 -oxidation of triplet phosphinidenes 61 and nitrenes 66 – 68 at 30 K, the O 2 -doped matrix containing H 2 NP was annealed to 30 K to allow O 2 diffusion for possible thermal reaction with H 2 NP. However, no reaction occurs to H 2 NP, which is consistent with the closed-shell singlet spin nature of H 2 NP, since its reaction with O 2 is spin forbidden. Molecular orbitals The frontier molecular orbitals of trans -HPNH, cis -HPNH, H₂NP, and H₂PN are depicted in Fig. 4 . In line with the double-bond characters of the PN moieties in these species, the lowest unoccupied molecular orbitals (LUMOs) correspond to the antibonding character of the PN bond. The highest occupied molecular orbitals (HOMOs) in trans -HPNH, cis -HPNH, and H₂NP show pronounced lone-pair character on the phosphorus atom, whereas, the HOMO in H₂PN is mainly composed by the lone-pair character on the nitrogen atom. The HOMO-1 and HOMO-2 for all the four species correspond to the π- and σ-bonding interactions of the PN moiety, respectively. In agreement with the high reactivity of these phosphorus-containing compounds, the natural bond orbital (NBO) calculations indicate significant polarization in the PN double bonds. The nitrogen atoms bear large negative partial charges of − 1.02 e , − 1.04 e , − 1.09 e , and − 0.88 e , while the phosphorus atoms carry positive charges of + 0.77 e , + 0.82 e , + 0.33 e , and + 0.98 e for trans -HPNH, cis -HPNH, H 2 NP, and H 2 PN, respectively. Conclusion In conclusion, the prototype phosphorus-nitrogen compound HPNH in the cis and trans conformations has been generated in the gas phase and characterized with IR and UV-vis spectroscopy in N 2 -matrices at 10 K. In addition to the photo-induced cis ⇄ trans conformational interconversion, the photochemistry of HPNH at 395 nm in the matrix reveals isomerization to the long sought-after aminophosphinidene H 2 NP in the singlet ground state. The first time observation of these prototype species complements the fundamental knowledge of phosphorus-nitrogen compounds. Considering the previously proposed possible involvement of the [2H, N, P] isomers in the astrochemical network of the important phosphorus-bearing species PN in the interstellar medium (ISM), the disclosed photoreactivity of these isomers including the reactions of H 2 NP with CO and O 2 could be of interest in understanding the interstellar phosphorus chemistry. Methods Sample preparation. Di- tert -butylaminophosphane (( t -Bu) 2 PNH 2 ) was synthesized by reaction of ( t- Bu) 2 PCl (97%, Adamas) with NH 3 (99%, Wetry) according to the published protocol. 69 The purity of ( t -Bu) 2 PNH 2 was checked with 31 P NMR spectroscopy (Fig. S9). For the 15 N- and D-labeled ( t -Bu) 2 PNH 2 , 15 NH 3 and ND 3 gases were used. 15 NH 3 was synthesized by heating the mixture of Ca(OH) 2 and NH 4 Cl (99% atom 15 N, Cambridge) with an alcohol burner, and ND 3 is commercially available. Matrix‑isolation IR and UV-vis spectroscopy. The setups for matrix-isolation experiments were described before. [49] Briefly, matrix-isolation IR spectra were recorded at resolution of 0.5 cm − 1 on an FT-IR spectrometer (Bruker 70 V). To prepare the matrix, gaseous samples were mixed by passing a flow of matrix gas (N 2 ) through a cold U-trap (–20°C) containing ca. 20 mg of freshly synthesized ( t- Bu) 2 PNH 2 . Then the mixture of ( t- Bu) 2 PNH 2 vapor/N 2 (~ 1:1000 estimated) was passed through an Al 2 O 3 tube furnace (o.d. 2.0 mm, i.d. 1.0 mm), which can be heated over a length of ca. 30 mm by a tantalum wire (resistance 2.9 Ω, voltage 10.0 V, and current 3.50 A). The resulting pyrolysis products were deposited (2 mmol h − 1 ) onto the gold-plated copper block matrix support (10 K) in a high vacuum (∼10 − 6 Pa) using a closed-cycle helium cryostat (Sumitomo Heavy Industries, SRDK-408D2-F50H) inside the chamber. Matrix-isolation UV-vis spectra were recorded on a PerkinElmer Lambda 850 + spectrometer (190–600 nm, scanning speed of 1 nm s − 1 ). The high-vacuum flash pyrolysis products were deposited onto a CaF 2 matrix support (10 K) for the measurements. Photolysis experiments were performed by using UV flashlight LEDs including 410 nm (10 W), 395 nm (15 W), 365 nm (15 W), and 310 nm (15 W). Quantum chemistry calculation. Structures and IR frequencies for stationary points and transition states of the [2H, P, N] system were initially calculated at the DSD-PBEP86/aug-cc-pVTZ level of theory. 70 For the calculations on the decomposition of ( t- Bu) 2 PNH 2 , the B3LYP/6-311 + + G(3df,3pd) 71,72 method was used. Local minima were confirmed by vibrational frequency analysis, and the transition states were ascertained with additional intrinsic reaction coordinate (IRC) calculations. 73 These calculations were performed using the Gaussian 16 software package. 74 Time-dependent (TD) 75 calculations at the DSD-PBEP86/aug-cc-pVTZ level was performed for the prediction of UV-vis transitions energies. Single-point energies were corrected at the CCSD(T)/CBS level. 76 , 77 These calculations were performed using the ORCA 5.0 software package. 78 Further vibrational frequency calculations were carried out at the CCSD(T)-F12B/VTZ-F12 79,80 level using configuration-selective vibrational configuration interaction (VCI) 52 theory with Molpro 2019 package. 81 The NRT calculations were carried out with the NBO 6.0. 82 The molecular orbital graphs are rendered by the VMD 1.9.3 program. 83 Declarations Data availability IR spectra for the photochemistry of HPNH in matrices, 31 P NMR spectrum for ( t -Bu) 2 PNH 2 , quantum calculation results, and the atomic coordinates for all discussed species are provided in the Supplementary Information. Acknowledgement This work is supported by the National Natural Science Foundation of China (22025301, U23B20163, 22206027, and 22473030). Author contributions X.Z. conceived project and designed the experiments. J.J. performed the synthesis and spectroscopic measurements. L.W. and Y.G. also contributed to the spectroscopic measurements and analysis of the spectral data. J.J, Y.G., L.H. and G.R. carried out the quantum chemical calculations. L.W., J.J., and X.Z. discussed the results and drafted the manuscript. All authors commented on the manuscript. Competing interests The authors declare no competing interests. Additional information Supplementary information The online version contains supplementary material available at https://doi.org/ Correspondence and requests for materials should be addressed to Lina Wang and Xiaoqing Zeng. References Fischer, R. C. & Power, P. P. π-Bonding and the lone pair effect in multiple bonds involving heavier main group elements: Developments in the new millennium. Chem. Rev. 110 , 3877−3923 (2010). Velian, A. & Cummins, C. C. Synthesis and characterization of P 2 N 3 2- : An aromatic ion composed of phosphorus and nitrogen. Science 348 , 1001−1004 (2015). 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Chem. 63 , 287−323 (2012). Helgaker, T., Klopper, W., Koch, H. & Noga, J. Basis-set convergence of correlated calculations on water. J. Chem. Phys. 106 , 9639−9646 (1997). Neese, F. & Valeev, E. F. Revisiting the atomic natural orbital approach for basis sets: Robust systematic basis sets for explicitly correlated and conventional correlated ab initio methods? J. Chem. Theory Comput. 7 , 33−43 (2011). Neese, F. Software update: The ORCA program system—Version 5.0. Wires Comput. Mol. Sci. 12 , e1606 (2022). Adler, T. B., Knizia, G. & Werner, H.-J. A simple and efficient CCSD(T)-F12 approximation. J. Chem. Phys. 127 , 221106 (2007). Peterson, K. A., Adler, T. B. & Werner, H.-J. Systematically convergent basis sets for explicitly correlated wavefunctions: The atoms H, He, B–Ne, and Al–Ar. J. Chem. Phys. 128 , 084102 (2008). Werner, H.-J., Knowles, P. J., Knizia, G., Manby, F. R. & Schütz, M. Molpro: a general-purpose quantum chemistry program package. Wires Comput. Mol. Sci. 2 , 242−253 (2012). Glendening, E. D. et al. NBO 6.0. Theoretical Chemistry Institute, University of Wisconsin, Madison, 2013. Humphrey, W., Dalke, A. & Schulten, K. VMD: Visual molecular dynamics. J. Mol. Graph. 14 , 33−38 (1996). Schemes Schemes 1 and 2 are available in the Supplementary Files section. Additional Declarations There is NO Competing Interest. Supplementary Files Supplementaryinformation.pdf Supplementary Information Scheme1.png Scheme 1 | Relative energies (kcal mol−1, in parentheses) of the [2H, P, N] isomers calculated at the CCSD(T)/CBS level. Scheme2.png Scheme 2 | Synthetic route to HPNH by high-vacuum flash pyrolysis (HVFP) of ( t -Bu) 2 PNH 2 . 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-7398545","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":505395524,"identity":"cfa2b039-f3b3-4f99-9337-83c0ff14aa79","order_by":0,"name":"Xiaoqing Zeng","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA10lEQVRIiWNgGAWjYPACG34GhgQQg5loLWmSDaRqOUyCFoPj6Q8fF/w6L2FwPPnZA4YK68QG9rMH8GqR7HmQbDyz77aEwZln5gYMZ9ITG3jyEvBq4ZdIOCbN23O7zuBGgpkEY9vhxAYJHgO8WtgkEtt/8/ackzC4kf5NgvEfEVr4JZLZmHl+HABqyQHa0kCEFsmeZ8zSvA3JEpJn3pQBHZlu3MaTg18LKMQ+8/yxk+A7nr5N4kONtWw/+xn8WsCRztiGYDOwEVAPVfaHsLJRMApGwSgYwQAAYYhEu1Ah/nsAAAAASUVORK5CYII=","orcid":"https://orcid.org/0000-0003-4611-2094","institution":"Fudan University","correspondingAuthor":true,"prefix":"","firstName":"Xiaoqing","middleName":"","lastName":"Zeng","suffix":""},{"id":505395525,"identity":"ffc736b1-516b-409a-8ba6-24113be54652","order_by":1,"name":"Junjie Jiang","email":"","orcid":"","institution":"Fudan University","correspondingAuthor":false,"prefix":"","firstName":"Junjie","middleName":"","lastName":"Jiang","suffix":""},{"id":505395526,"identity":"3b0d992b-6e31-4ef7-987b-97a7250db7dc","order_by":2,"name":"Yixing Guo","email":"","orcid":"","institution":"Fudan University","correspondingAuthor":false,"prefix":"","firstName":"Yixing","middleName":"","lastName":"Guo","suffix":""},{"id":505395527,"identity":"59901a1b-ebca-4d61-84f9-9b029804ac29","order_by":3,"name":"Longtian Huang","email":"","orcid":"","institution":"Fudan University","correspondingAuthor":false,"prefix":"","firstName":"Longtian","middleName":"","lastName":"Huang","suffix":""},{"id":505395528,"identity":"9f70fd01-6956-4e25-9969-b7ed84c83218","order_by":4,"name":"Lina Wang","email":"","orcid":"","institution":"Fudan University","correspondingAuthor":false,"prefix":"","firstName":"Lina","middleName":"","lastName":"Wang","suffix":""},{"id":505395529,"identity":"06f47e4f-6683-4814-aa17-e10c6265928d","order_by":5,"name":"Guntram Rauhut","email":"","orcid":"","institution":"University of Stuttgart: Universitat Stuttgart","correspondingAuthor":false,"prefix":"","firstName":"Guntram","middleName":"","lastName":"Rauhut","suffix":""}],"badges":[],"createdAt":"2025-08-18 10:20:42","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-7398545/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-7398545/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1038/s41467-026-68391-7","type":"published","date":"2026-01-22T05:00:00+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":89911600,"identity":"5bb658c0-20ca-418b-a409-5b49dfad2e57","added_by":"auto","created_at":"2025-08-26 11:03:27","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":83740,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eGeneration and characterization of HPNH.\u003c/strong\u003e (A) IR spectrum (3400−800 cm\u003csup\u003e–1\u003c/sup\u003e) of the matrix-isolated pyrolysis (ca. 950 K) products of (\u003cem\u003et\u003c/em\u003e-Bu)\u003csub\u003e2\u003c/sub\u003ePNH\u003csub\u003e2\u003c/sub\u003e in a solid N\u003csub\u003e2\u003c/sub\u003e-matrix at 10 K. The IR bands for C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e8\u003c/sub\u003e (\u003cstrong\u003ec\u003c/strong\u003e) and C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e10\u003c/sub\u003e (\u003cstrong\u003ed\u003c/strong\u003e) are also marked. (B) IR difference spectrum showing the isomerization from \u003cem\u003etrans\u003c/em\u003e-HPNH (\u003cstrong\u003ea\u003c/strong\u003e) to \u003cem\u003ecis\u003c/em\u003e-HPNH (\u003cstrong\u003eb\u003c/strong\u003e) in the matrix upon photoexcitation at 410 nm (10 min). (C) IR difference spectrum showing the reverse conversion from \u003cem\u003ecis\u003c/em\u003e-HPNH (\u003cstrong\u003eb\u003c/strong\u003e) to \u003cem\u003etrans\u003c/em\u003e-HPNH (\u003cstrong\u003ea\u003c/strong\u003e) in the matrix upon subsequent photoexcitation at 365 nm (30 min).\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-7398545/v1/6bf594c367884d913991fb6e.png"},{"id":89913450,"identity":"9524bca6-18b3-4194-a8c0-77069bc17bb3","added_by":"auto","created_at":"2025-08-26 11:19:27","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":82951,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eGeneration and characterization of H\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eNP.\u003c/strong\u003e (A) UV-vis spectra of the N\u003csub\u003e2\u003c/sub\u003e-matrix isolated high-vacuum flash pyrolysis products of (\u003cem\u003et\u003c/em\u003e-Bu)\u003csub\u003e2\u003c/sub\u003ePNH\u003csub\u003e2\u003c/sub\u003e and also the photolysis products. Inset is the calculated vertical transitions at the TD-DSD-PBEP86/aug-cc-pVTZ level of theory. (B) IR difference spectrum (3400−700 cm\u003csup\u003e-1\u003c/sup\u003e) showing the isomerization from \u003cem\u003etrans-\u003c/em\u003e and\u003cem\u003e cis\u003c/em\u003e-HPNH (\u003cstrong\u003ea\u003c/strong\u003e and \u003cstrong\u003eb\u003c/strong\u003e) to H\u003csub\u003e2\u003c/sub\u003eNP (\u003cstrong\u003ee\u003c/strong\u003e) upon photoexcitation at 395 nm (10 min) in the N\u003csub\u003e2\u003c/sub\u003e-matrix at 10 K. (C) IR difference spectrum showing the reverse isomerization from H\u003csub\u003e2\u003c/sub\u003eNP (\u003cstrong\u003ee\u003c/strong\u003e) to \u003cem\u003etrans-\u003c/em\u003e and\u003cem\u003e cis\u003c/em\u003e-HPNH (\u003cstrong\u003ea\u003c/strong\u003e and \u003cstrong\u003eb\u003c/strong\u003e) upon subsequent photoexcitation at 310 nm (10 min) in the matrix at 10 K.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-7398545/v1/a8286037a5546fc0a8068c24.png"},{"id":89911597,"identity":"db64ac46-1978-463d-9d37-5328ad37ff11","added_by":"auto","created_at":"2025-08-26 11:03:27","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":70168,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003ePhotoreactions of H\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eNP. \u003c/strong\u003e(A) IR difference spectrum (3600−700 cm\u003csup\u003e−1\u003c/sup\u003e) showing the photochemistry of HPNH upon photoexcitation at 395 nm (10 min) in pure CO solid at 10 K. (B) IR difference spectrum showing the photochemistry of HPNH in an O\u003csub\u003e2\u003c/sub\u003e-doped (5%) N\u003csub\u003e2\u003c/sub\u003e-matrix upon photoexcitation at 395 nm (10 min). The IR bands for \u003cem\u003etrans\u003c/em\u003e-HPNH (a), \u003cem\u003ecis\u003c/em\u003e-HPNH (b), H\u003csub\u003e2\u003c/sub\u003eNP (e), H\u003csub\u003e2\u003c/sub\u003eNPCO (f), and H\u003csub\u003e2\u003c/sub\u003eNPO\u003csub\u003e2\u003c/sub\u003e (g) and unknown species (*) are marked. (C) Photochemistry of H\u003csub\u003e2\u003c/sub\u003eNP.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-7398545/v1/36b3b9fd9233c0ea0284e043.png"},{"id":89911601,"identity":"fe3f233a-f6ea-428f-be6f-ea98c582b9ae","added_by":"auto","created_at":"2025-08-26 11:03:27","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":290039,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eThe DSD-PBEP86/aug-cc-pVTZ calculated frontier molecular orbitals (isovalue = 0.04) and energies for HPNH, H\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eNP, and H\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003ePN exhibiting P–N multiple bonding properties.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-7398545/v1/7b4b5e42c158948ddbb22af0.png"},{"id":102822612,"identity":"24a40b03-9e6a-42d3-85bd-eed0b8be7784","added_by":"auto","created_at":"2026-02-17 08:08:22","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1731273,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-7398545/v1/74e10934-3d70-4456-8129-017e3132e562.pdf"},{"id":89911603,"identity":"2d5c6e49-7425-43ef-be10-082020c36bfe","added_by":"auto","created_at":"2025-08-26 11:03:27","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":4404260,"visible":true,"origin":"","legend":"Supplementary Information","description":"","filename":"Supplementaryinformation.pdf","url":"https://assets-eu.researchsquare.com/files/rs-7398545/v1/51a7e7259bfa3b1dbe970a18.pdf"},{"id":89911596,"identity":"f70d0d7a-f7f1-4156-b471-9d611aae0ee2","added_by":"auto","created_at":"2025-08-26 11:03:27","extension":"png","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":19545,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eScheme 1 | Relative energies (kcal mol−1, in parentheses) of the [2H, P, N] isomers calculated at the CCSD(T)/CBS level.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"Scheme1.png","url":"https://assets-eu.researchsquare.com/files/rs-7398545/v1/e9cf8323d7bbfc80f2bad36e.png"},{"id":89911598,"identity":"de620a8d-b669-4301-9152-5b3e92a0401a","added_by":"auto","created_at":"2025-08-26 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\"/\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eScheme 2 | Synthetic route to HPNH by high-vacuum flash pyrolysis (HVFP) of (\u003c/strong\u003e\u003cem\u003e\u003cstrong\u003et\u003c/strong\u003e\u003c/em\u003e\u003cstrong\u003e-Bu)\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003ePNH\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"Scheme2.png","url":"https://assets-eu.researchsquare.com/files/rs-7398545/v1/c83fb50d33bf97497c70ddce.png"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"\u003cp\u003e\u003cstrong\u003eThe Simplest Iminophosphane HPNH and Its Photoisomerization to Aminophosphinidene H\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eNP\u003c/strong\u003e\u003c/p\u003e","fulltext":[{"header":"Introduction","content":"\u003cp\u003eThe chemistry of multiply bonded compounds involving group 15 elements keeps attracting enormous interest, not only due to the novel structural and bonding properties but also their broad applications in synthetic chemistry and materials science.\u003csup\u003e\u003cspan additionalcitationids=\"CR2\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e\u003c/sup\u003e Particularly, an extremely important role in the main group chemistry has been played by low-valent phosphorus. As a heavy analogue to molecular nitrogen (N\u003csub\u003e2\u003c/sub\u003e), the diatomic phosphorus mononitride (PN) was first spectroscopically detected in the gas phase in 1933.\u003csup\u003e\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e\u003c/sup\u003e Chemically, PN is very reactive, and it aggregates spontaneously above 10 K to form polymeric (PN)\u003csub\u003en\u003c/sub\u003e\u003csup\u003e\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e,\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e\u003c/sup\u003e and the H\u0026uuml;ckel aromatic cyclotriphosphazene P\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e3\u003c/sub\u003e.\u003csup\u003e\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e,\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e\u003c/sup\u003e As the first phosphorus-containing species detected in the interstellar medium,\u003csup\u003e\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e,\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e\u003c/sup\u003e PN plays a key role in the chemical network of phosphorus astrochemistry.\u003csup\u003e\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e\u003c/sup\u003e Quite recently, PN and another small phosphorus compound \u0026bull;PO were observed in the dense molecular cloud WB89-621 at the edge of the Galaxy.\u003csup\u003e\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e,\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e\u003c/sup\u003e Considering the essential role of the phosphorus element in the origin and evolution of life, the prebiotic chemistry of PN\u003csup\u003e\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e,\u003cspan additionalcitationids=\"CR15\" citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e\u003c/sup\u003e and other astronomically detected P-bearing molecules such as \u0026bull;PO,\u003csup\u003e\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e\u003c/sup\u003e PH\u003csub\u003e3\u003c/sub\u003e,\u003csup\u003e\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e\u003c/sup\u003e and HCP\u003csup\u003e\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u003c/sup\u003e have been extensively explored. To explore the synthetic applications, stable compounds containing terminal PN unit have been synthesized and used as precursors for the release of PN under catalytic conditions.\u003csup\u003e\u003cspan additionalcitationids=\"CR21 CR22 CR23\" citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e\u003cp\u003eAs the simple derivatives of PN, the three isomers HPNH, H\u003csub\u003e2\u003c/sub\u003eNP, and H\u003csub\u003e2\u003c/sub\u003ePN serve as prototype molecules consisting of phosphorus-nitrogen multiple bonds. Particularly, HPNH is the simplest iminophosphane that has been proposed as a candidate interstellar species, which could be formed through hydrogenation of PN via intermediacy of the HPN\u0026bull; and HNP\u0026bull; radicals.\u003csup\u003e\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e,\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e\u003c/sup\u003e The structural and bonding properties of HPNH have been extensively explored\u003csup\u003e\u003cspan additionalcitationids=\"CR28 CR29 CR30\" citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e\u003c/sup\u003e by quantum chemical calculations since the first theoretical study by Trinquier in 1982.\u003csup\u003e\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e\u003c/sup\u003e Theoretically, HPNH can exist in planar \u003cem\u003etrans\u003c/em\u003e or \u003cem\u003ecis\u003c/em\u003e conformations, and the former is slightly lower in energy by 1 kcal mol\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e (Scheme \u003cspan refid=\"Sch1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). Moreover, \u003cem\u003etrans-\u003c/em\u003eHPNH (\u003cem\u003etrans\u003c/em\u003e-\u003cb\u003e1\u003c/b\u003e, Scheme \u003cspan refid=\"Sch1\" class=\"InternalRef\"\u003e1\u003c/span\u003e) is the global minimum on the potential energy surface of the [2H, P, N] system, and its thermal stability is secured with the large barriers (\u0026gt;\u0026thinsp;60 kcal mol\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e) for its isomerization to the two less stable isomers H\u003csub\u003e2\u003c/sub\u003eNP (\u003cb\u003e3\u003c/b\u003e) and H\u003csub\u003e2\u003c/sub\u003ePN (\u003cb\u003e2\u003c/b\u003e) via 1,2-hydrogen migration. However, all the early attempts to generate HPNH were unsuccessful,\u003csup\u003e\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e\u003c/sup\u003e whereas, a number of the sterically protected and the carbene-stabilized iminophosphanes has been synthesized and broadly used in organophosphorus chemistry.\u003csup\u003e\u003cspan additionalcitationids=\"CR35 CR36 CR37 CR38 CR39\" citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e\u003c/sup\u003e Among the [2H, P, N] isomers, the least stable isomer H\u003csub\u003e2\u003c/sub\u003ePN features as the parent phosphinonitrene, and it was calculated to have closed-shell singlet ground state (\u003cem\u003esinglet\u003c/em\u003e-\u003cb\u003e2\u003c/b\u003e) due to electron delocalization of the lone pair electrons, leading to a strongly polarized shorter PN double bond than those in HPNH. In contrast, the triplet state (\u003cem\u003etriplet\u003c/em\u003e-\u003cb\u003e2\u003c/b\u003e) is less stable by 16.7 kcal mol\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e. Experimentally, H\u003csub\u003e2\u003c/sub\u003ePN has so far resisted all attempts at its detection including the recent attempted generation from photodecomposition of H\u003csub\u003e2\u003c/sub\u003ePNCO.\u003csup\u003e\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e\u003c/sup\u003e Notably, singlet phosphinonitrenes stabilized by sterically demanding substituents have been synthesized\u003csup\u003e\u003cspan additionalcitationids=\"CR42\" citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e\u003c/sup\u003e and used for the activation of small molecules.\u003csup\u003e\u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eIn contrast to the large singlet-triplet energy gap for H\u003csub\u003e2\u003c/sub\u003ePN, the ground-state spin multiplicity of the isomeric H\u003csub\u003e2\u003c/sub\u003eNP remains unclear as the sign for the predicted singlet-triplet energy gap depends on the theoretical methods.\u003csup\u003e\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e,\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e,\u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e\u003c/sup\u003e According to the most recent calculations by Schaefer III et al.,\u003csup\u003e\u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e\u003c/sup\u003e the singlet state is slightly lower by 0.2 kcal mol\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e due to effective electron delocalization of the lone pair electrons in the singlet state (\u003cem\u003esinglet\u003c/em\u003e-\u003cb\u003e3\u003c/b\u003e), and it contains an ideal phosphorus-nitrogen double bond with a bond order of 2, whereas, \u003cem\u003etriplet\u003c/em\u003e-\u003cb\u003e3\u003c/b\u003e features a smaller bond order of 1.5. Similar to the elusiveness of HPNH and H\u003csub\u003e2\u003c/sub\u003ePN, recent attempts to generate H\u003csub\u003e2\u003c/sub\u003eNP from photodecomposition of H\u003csub\u003e2\u003c/sub\u003eNPCO in cryogenic matrix\u003csup\u003e\u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e47\u003c/span\u003e\u003c/sup\u003e and thermal decomposition of a dibenzo-7-phosphanorbornadiene precursor in the gas phase\u003csup\u003e\u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e48\u003c/span\u003e\u003c/sup\u003e were unsuccessful. This is in sharp contrast to the analogous systems H\u003csub\u003e2\u003c/sub\u003ePP/HPPH\u003csup\u003e49\u003c/sup\u003e and H\u003csub\u003e2\u003c/sub\u003eNN/HNNH,\u003csup\u003e50\u003c/sup\u003e which have already been well characterized. Herein, we report the first time preparation and characterization of \u003cem\u003ecis-\u003c/em\u003eHPNH, \u003cem\u003etrans-\u003c/em\u003eHPNH, and H\u003csub\u003e2\u003c/sub\u003eNP in cryogenic matrices at 10 K. In addition to the photo-induced interconversion among these isomers, the photoreactions of H\u003csub\u003e2\u003c/sub\u003eNP with CO and O\u003csub\u003e2\u003c/sub\u003e have also been studied.\u003c/p\u003e"},{"header":"Results and Discussion","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e\u003ch2\u003eGeneration and characterization of HPNH\u003c/h2\u003e\u003cp\u003eThe preparation of HPNH was performed by high-vacuum flash pyrolysis (HVFP) of di-\u003cem\u003etert\u003c/em\u003e-butylphosphanamine ((\u003cem\u003et\u003c/em\u003e-Bu)\u003csub\u003e2\u003c/sub\u003ePNH\u003csub\u003e2\u003c/sub\u003e) in the gas phase at ca. 950 K (Scheme \u003cspan refid=\"Sch2\" class=\"InternalRef\"\u003e2\u003c/span\u003e). A typical IR spectrum for the thermolysis products isolated in a solid N\u003csub\u003e2\u003c/sub\u003e-matrix at 10 K (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eA) shows IR bands of the fragments C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e8\u003c/sub\u003e and C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e10\u003c/sub\u003e,\u003csup\u003e\u003cspan citationid=\"CR51\" class=\"CitationRef\"\u003e51\u003c/span\u003e\u003c/sup\u003e along with some weak bands of the counterpart fragment HPNH. When using the deuterated precursor (\u003cem\u003et\u003c/em\u003e-Bu)\u003csub\u003e2\u003c/sub\u003ePND\u003csub\u003e2\u003c/sub\u003e, the mono-deuterated dissociation products HPND and [D\u003csub\u003e1\u003c/sub\u003e]-C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e10\u003c/sub\u003e were identified (Fig. S2), implying that the dissociation of (\u003cem\u003et\u003c/em\u003e-Bu)\u003csub\u003e2\u003c/sub\u003ePNH\u003csub\u003e2\u003c/sub\u003e likely proceeds in a stepwise pathway (Scheme \u003cspan refid=\"Sch2\" class=\"InternalRef\"\u003e2\u003c/span\u003e).\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eConsidering the TD-DSD-PBEP86/aug-cc-pVTZ calculated absorption at 432 nm for the π* \u0026larr; n transition in \u003cem\u003etrans\u003c/em\u003e-HPNH (Table \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e), the matrix containing the pyrolysis products of (\u003cem\u003et\u003c/em\u003e-Bu)\u003csub\u003e2\u003c/sub\u003ePNH\u003csub\u003e2\u003c/sub\u003e was subjected to the irradiation at 410 nm. The resulting IR difference spectrum (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eB) reflecting the changes of the matrix shows selective depletion of \u003cem\u003etrans\u003c/em\u003e-HPNH with a group of IR bands at 3309.1, 2225.0, 1107.0, 1012.8, 953.5, and 911.0 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e along with the concomitant appearance of another group of IR bands at 3334.2, 2135.2, 1074.8, 1023.5, 897.4, and 816.9 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e for \u003cem\u003ecis\u003c/em\u003e-HPNH. Notably, the IR bands for \u003cem\u003ecis\u003c/em\u003e-HPNH are also detectable in the spectrum of the decomposition products of the precursor, indicating that both conformers of HPNH were produced in the gas phase. To aid the identification, quantum chemical calculations on the IR spectra for the two conformers of HPNH (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e) were carried out at the CCSD(T)-F12B/VTZ-F12 level of theory using configuration-selective vibrational configuration interaction theory (VCI).\u003csup\u003e\u003cspan citationid=\"CR52\" class=\"CitationRef\"\u003e52\u003c/span\u003e\u003c/sup\u003e Additionally, isotope labeling experiment was performed by using (\u003cem\u003et\u003c/em\u003e-Bu)\u003csub\u003e2\u003c/sub\u003eP\u003csup\u003e\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003eNH\u003csub\u003e2\u003c/sub\u003e as the precursor to HP\u003csup\u003e\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003eNH (Figs. S1 and S5).\u003c/p\u003e\u003cp\u003e\u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e\u003ccaption language=\"En\"\u003e\u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e\u003cdiv class=\"CaptionContent\"\u003e\u003cp\u003e\u003cb\u003eCalculated and observed IR data for the two conformers of HPNH.\u003c/b\u003e\u003c/p\u003e\u003c/div\u003e\u003c/caption\u003e\u003ccolgroup cols=\"13\"\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c8\" colnum=\"8\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c9\" colnum=\"9\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c10\" colnum=\"10\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c11\" colnum=\"11\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c12\" colnum=\"12\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c13\" colnum=\"13\"\u003e\u003c/div\u003e\u003cthead\u003e\u003ctr\u003e\u003cth align=\"left\" colspan=\"6\" nameend=\"c6\" namest=\"c1\"\u003e\u003cp\u003e\u003cem\u003ecis-\u003c/em\u003eHPNH\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colspan=\"6\" nameend=\"c12\" namest=\"c7\"\u003e\u003cp\u003e\u003cem\u003etrans-\u003c/em\u003eHPNH\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c13\"\u003e\u003cp\u003emode\u003csup\u003e[e]\u003c/sup\u003e\u003c/p\u003e\u003c/th\u003e\u003c/tr\u003e\u003c/thead\u003e\u003ctbody\u003e\u003ctr\u003e\u003ctd align=\"left\" colspan=\"2\" nameend=\"c2\" namest=\"c1\"\u003e\u003cp\u003eν\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colspan=\"2\" nameend=\"c4\" namest=\"c3\"\u003e\u003cp\u003eΔν(H/D)\u003csup\u003e[c]\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colspan=\"2\" nameend=\"c6\" namest=\"c5\"\u003e\u003cp\u003eΔν(\u003csup\u003e14/15\u003c/sup\u003eN)\u003csup\u003e[d]\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colspan=\"2\" nameend=\"c8\" namest=\"c7\"\u003e\u003cp\u003eν\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colspan=\"2\" nameend=\"c10\" namest=\"c9\"\u003e\u003cp\u003eΔν(H/D)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colspan=\"2\" nameend=\"c12\" namest=\"c11\"\u003e\u003cp\u003eΔν(\u003csup\u003e14/15\u003c/sup\u003eN)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eCal.\u003csup\u003e[a]\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003eObs.\u003csup\u003e[b]\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003eCal.\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003eObs.\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003eCal.\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003eObs.\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003eCal.\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003eObs.\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003eCal.\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003eObs.\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003eCal.\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003eObs.\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003e3345.5 (7)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e3334.2 (39)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e\u0026minus;862.3\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e\u0026minus;863.7\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e\u0026minus;7.4\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e\u0026minus;7.4\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e3299.5 (8)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e3309.1 (40)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e\u0026minus;851.2\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e\u0026minus;844.3\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e\u0026minus;6.6\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e\u0026minus;7.1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003eν\u003csub\u003e1\u003c/sub\u003e, ν(NH)\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003e2120.3 (147)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e2135.3 (100)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e\u0026minus;3.1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e\u0026minus;0.2\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e2212.9 (123)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e2225.0 (100)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e+\u0026thinsp;0.4\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e+\u0026thinsp;0.5\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003eν\u003csub\u003e2\u003c/sub\u003e, ν(PH)\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003e1022.4 (31)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e1023.5 (47)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e\u0026minus;31.0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e\u0026minus;29.2\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e\u0026minus;13.2\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e\u0026minus;12.1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e1096.8 (23)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e1107.0 (33)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e\u0026minus;42.4\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e\u0026minus;37.0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e\u0026minus;8.4\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e\u0026minus;8.5\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003eν\u003csub\u003e3\u003c/sub\u003e, δ(NH)\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003e1073.2 (5)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e1074.8 (7)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e\u0026minus;36.5\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e\u0026minus;33.8\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e\u0026minus;11.7\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e\u0026minus;11.8\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e1005.7 (50)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e1012.8 (89)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e\u0026minus;13.6\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e\u0026minus;8.2\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e\u0026minus;18.2\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e\u0026minus;18.9\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003eν\u003csub\u003e4\u003c/sub\u003e, ν(PN)\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003e897.0 (68)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e897.4 (83)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e\u0026minus;150.3\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e\u0026minus;148.8\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e\u0026minus;2.8\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e\u0026minus;2.9\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e951.6 (27)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e953.5 (43)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e\u0026minus;164.5\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e\u0026minus;160.0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e\u0026minus;1.7\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e\u0026minus;1.8\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003eν\u003csub\u003e6\u003c/sub\u003e, δ(HPNH)\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003e807.4 (84)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e816.9 (87)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e\u0026minus;171.7\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e\u0026minus;173.6\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e\u0026minus;2.3\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e\u0026minus;2.0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e895.0 (40)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e911.0 (80)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e\u0026minus;198.4\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e\u0026minus;204.6\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e\u0026minus;0.6\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e\u0026minus;0.7\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003eν\u003csub\u003e5\u003c/sub\u003e, δ(HPNH)\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003c/tbody\u003e\u003c/colgroup\u003e\u003c/table\u003e\u003c/div\u003e\u003c/p\u003e\u003cp\u003e[a] Calculated IR frequencies and intensities (km mol\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e, in parentheses) at the CCSD(T)-F12B/VTZ-F12 level of theory using configuration-selective vibrational configuration interaction theory (VCI). [b] Observed band position (cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e) for the strongest matrix site in N\u003csub\u003e2\u003c/sub\u003e-matrix at 10 K. [c] Calculated and observed D-isotopic shifts for HPND. [d] Calculated and observed \u003csup\u003e\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003eN-isotopic shifts for HP\u003csup\u003e\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003eNH. [e] Assignment of the vibrational modes.\u003c/p\u003e\u003cp\u003eIn the IR spectrum of \u003cem\u003etrans\u003c/em\u003e-HPNH, the band at 3309.1 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e shows D- and \u003csup\u003e\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003eN-isotopic shifts of \u0026minus;\u0026thinsp;844.3 and \u0026minus;\u0026thinsp;7.1 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e, respectively, supporting its assignment to the NH stretching mode with a calculated frequency of 3299.5 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e. The frequency is lower than that in \u003cem\u003ecis\u003c/em\u003e-HPNH (obs. 3334.2 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e; cal. 3345.5 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e), for which the D- and \u003csup\u003e\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003eN-isotopic shifts are \u0026minus;\u0026thinsp;863.7 and \u0026minus;\u0026thinsp;7.4 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e, respectively. The NH stretching frequencies in the two conformers of HPNH are close to the same mode in HNSO (3308.5 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e).\u003csup\u003e\u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e53\u003c/span\u003e,\u003cspan citationid=\"CR54\" class=\"CitationRef\"\u003e54\u003c/span\u003e\u003c/sup\u003e The frequency for the PH stretching mode in \u003cem\u003etrans\u003c/em\u003e-HPNH (obs. 2225.0 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e; cal. 2212.9 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e) is significantly higher than that in \u003cem\u003ecis\u003c/em\u003e-HPNH (obs. 2135.0 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e; cal. 2120.3 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e), whereas, both are lower than the same mode in HPCO (2311.8 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e)\u003csup\u003e\u003cspan citationid=\"CR55\" class=\"CitationRef\"\u003e55\u003c/span\u003e,\u003cspan citationid=\"CR56\" class=\"CitationRef\"\u003e56\u003c/span\u003e\u003c/sup\u003e and HPNN (2322.1 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e).\u003csup\u003e\u003cspan citationid=\"CR57\" class=\"CitationRef\"\u003e57\u003c/span\u003e,\u003cspan citationid=\"CR58\" class=\"CitationRef\"\u003e58\u003c/span\u003e\u003c/sup\u003e The band at 1012.8 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e with a large \u003csup\u003e\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003eN-isotopic shift of \u0026minus;\u0026thinsp;18.9 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e for \u003cem\u003etrans\u003c/em\u003e-HPNH mainly involves the PN stretching vibration, and it couples with the NH bending at 1107.0 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e as evidenced by the \u003csup\u003e\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003eN-isotopic shift of \u0026minus;\u0026thinsp;8.5 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e. This vibrational coupling becomes more evident in the \u003cem\u003ecis\u003c/em\u003e conformer due to the nearly equivalent \u003csup\u003e\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003eN-isotopic shifts of \u0026minus;\u0026thinsp;11.8 and \u0026minus;\u0026thinsp;12.1 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e for the two bands at 1074.8 and 1023.5 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e, respectively. The PN stretching frequencies in the two conformers of HPNH are lower than those in FPNF (1116.8 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e, Δν(\u003csup\u003e14/15\u003c/sup\u003eN)\u0026thinsp;=\u0026thinsp;\u0026minus;\u0026thinsp;25.3 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e)\u003csup\u003e\u003cspan citationid=\"CR59\" class=\"CitationRef\"\u003e59\u003c/span\u003e\u003c/sup\u003e and HNP\u0026bull; (1136.3 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e, Δν(\u003csup\u003e14/15\u003c/sup\u003eN)\u0026thinsp;=\u0026thinsp;\u0026minus;\u0026thinsp;22.7 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e).\u003csup\u003e\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e\u003c/sup\u003e The last two bands for HPNH belong to the out-of-plane and in-plane deformation modes of the PH and NH moieties, respectively. Additionally, two very weak bands at 2207.6 and 2086.5 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e show similar changes with the other bands of \u003cem\u003etrans\u003c/em\u003e-HPNH and \u003cem\u003ecis\u003c/em\u003e-HPNH, respectively, and they belong to the ν\u003csub\u003e3\u003c/sub\u003e overtone of \u003cem\u003etrans\u003c/em\u003e-HPNH and the ν\u003csub\u003e3\u003c/sub\u003e\u0026thinsp;+\u0026thinsp;ν\u003csub\u003e4\u003c/sub\u003e combination of \u003cem\u003ecis\u003c/em\u003e-HPNH according to the corresponding D- and \u003csup\u003e\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003eN-isotopic shifts, as well as the theoretically predicted anharmonic frequencies of 2198.0 and 2083.0 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e, respectively. In line with the calculated absorption at 376 nm for \u003cem\u003ecis\u003c/em\u003e-HPNH (Table \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e), the reverse \u003cem\u003ecis\u003c/em\u003e to \u003cem\u003etrans\u003c/em\u003e conformational transformation in HPNH was observed upon subsequent photoexcitation at 365 nm (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eC).\u003c/p\u003e\u003cp\u003eConsistent with the \u003cem\u003etrans\u003c/em\u003e-HPNH \u0026rarr; \u003cem\u003ecis\u003c/em\u003e-HPNH photoisomerization observed by matrix-isolation IR spectroscopy, a weak absorption at around 420 nm in the UV-vis spectrum of the matrix-isolated HVFP products of (\u003cem\u003et\u003c/em\u003e-Bu)\u003csub\u003e2\u003c/sub\u003ePNH\u003csub\u003e2\u003c/sub\u003e was depleted by the irradiation at 410 nm, leading to the concomitant increase of another very weak absorption at around 340 nm (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eA). The assignment of the visible absorption (ca. 420 nm) to \u003cem\u003etrans\u003c/em\u003e-HPNH is supported by the good agreement with the calculated transition at 432 nm (Table \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e) for the excitation of the phosphorus lone-pair electron to the anti-bonding π* orbital. The UV-absorption (ca. 340 nm) corresponds to the similar transition of the \u003cem\u003ecis\u003c/em\u003e conformer with a calculated band at 376 nm.\u003c/p\u003e\u003c/div\u003e\n\u003ch3\u003ePhotoisomerization of HPNH to HNP\u003c/h3\u003e\n\u003cp\u003eIn addition to the photo-induced conformational rotation in HPNH, further photoexcitation of HPNH at 395 nm promotes 1,2-H migration to yield H\u003csub\u003e2\u003c/sub\u003eNP with IR bands at 3386.3, 3313.4, 947.6, 943.2, and 739.8 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eB). Accordingly, the absorptions for HPNH (\u003cem\u003ecis\u003c/em\u003e and \u003cem\u003etrans\u003c/em\u003e) decrease in the UV-vis spectrum (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eA). Consequently, new absorptions at 290 and 240 nm for the isomer H\u003csub\u003e2\u003c/sub\u003eNP appear (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eA), and they are in good agreement with the calculated vertical transitions at 302 and 232 nm for H\u003csub\u003e2\u003c/sub\u003eNP in the singlet state (Table \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e). Consistent with the observed absorption at 290 nm for H\u003csub\u003e2\u003c/sub\u003eNP, subsequent irradiation of the matrix at 310 nm causes reformation HPNH from H\u003csub\u003e2\u003c/sub\u003eNP (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eC).\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eThe photolytic interconversion between HPNH (\u003cem\u003ecis\u003c/em\u003e and \u003cem\u003etrans\u003c/em\u003e) and H\u003csub\u003e2\u003c/sub\u003eNP under the matrix-isolation conditions enables unambiguous identification of the weak IR bands for H\u003csub\u003e2\u003c/sub\u003eNP. The two bands at 3386.3 and 3313.4 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e with D-isotopic shifts of \u0026minus;\u0026thinsp;33.1 and \u0026minus;\u0026thinsp;829.9 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e in H(D)NP are reasonably assigned to the NH\u003csub\u003e2\u003c/sub\u003e stretching modes, and they show better agreement with the VCI calculated values for H\u003csub\u003e2\u003c/sub\u003eNP in the singlet state (3379.9 and 3322.2 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e) than those in the triplet state (3493.1 and 3423.9 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e, Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e). In accordance with the VCI calculated frequencies of 951.6 and 949.4 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e for the NH\u003csub\u003e2\u003c/sub\u003e deformation and NP stretching modes in singlet H\u003csub\u003e2\u003c/sub\u003eNP, two bands at 947.6 and 943.2 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e are observable in the IR difference spectrum (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eC). However, the VCI calculated frequencies for the same modes in triplet H\u003csub\u003e2\u003c/sub\u003eNP (845.6 and 813.9 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e) differ from the singlet state by more than 100 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e. Additionally, the NH\u003csub\u003e2\u003c/sub\u003e wagging mode locates at 739.8 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e (cal. 723.0 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e) as a broad band, and it shows a large D-isotopic shift of \u0026minus;\u0026thinsp;74.5 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e (cal. \u0026minus;74.5 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e) in H(D)NP.\u003c/p\u003e\u003cp\u003e\u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab2\" border=\"1\"\u003e\u003ccaption language=\"En\"\u003e\u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e\u003cdiv class=\"CaptionContent\"\u003e\u003cp\u003eCalculated and observed IR data for H\u003csub\u003e2\u003c/sub\u003eNP.\u003c/p\u003e\u003c/div\u003e\u003c/caption\u003e\u003ccolgroup cols=\"8\"\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c8\" colnum=\"8\"\u003e\u003c/div\u003e\u003cthead\u003e\u003ctr\u003e\u003cth align=\"left\" colspan=\"3\" nameend=\"c3\" namest=\"c1\"\u003e\u003cp\u003eν\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e\u003cp\u003eΔν(H/D)\u003csup\u003e[c]\u003c/sup\u003e\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e\u003cp\u003eΔν(\u003csup\u003e14/15\u003c/sup\u003eN)\u003csup\u003e[d]\u003c/sup\u003e\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c8\"\u003e\u003cp\u003emode\u003csup\u003e[e]\u003c/sup\u003e\u003c/p\u003e\u003c/th\u003e\u003c/tr\u003e\u003c/thead\u003e\u003ctbody\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003etriplet\u003csup\u003e[a]\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003esinglet\u003csup\u003e[a]\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003eObs.\u003csup\u003e[b]\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003eCal.\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003eObs.\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003eCal.\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003eObs.\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003e3493.1 (37)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e3379.9 (33)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e3386.3 (27)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e\u0026minus;30.9\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e\u0026minus;33.1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e\u0026minus;9.8\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e\u0026minus;9.4\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003eν\u003csub\u003e1\u003c/sub\u003e, ν\u003csub\u003eas\u003c/sub\u003e(NH\u003csub\u003e2\u003c/sub\u003e)\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003e3423.9 (25)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e3322.2 (\u0026lt;\u0026thinsp;1)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e3313.4 (1)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e\u0026minus;838.7\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e\u0026minus;829.9\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e\u0026minus;4.8\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e\u0026minus;6.0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003eν\u003csub\u003e2\u003c/sub\u003e, ν\u003csub\u003es\u003c/sub\u003e(NH\u003csub\u003e2\u003c/sub\u003e)\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003e1558.3 (20)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e1608.2 (2)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003en.o.\u003csup\u003e[f]\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e\u0026minus;167.4\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003en.o.\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e\u0026minus;5.7\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003en.o.\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003eν\u003csub\u003e3\u003c/sub\u003e, δ(NH\u003csub\u003e2\u003c/sub\u003e)\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003e845.6 (76)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e951.6 (33)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e947.6 (6)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e\u0026minus;3.1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003en.o.\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e\u0026minus;18.2\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003en.o.\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003eν\u003csub\u003e4\u003c/sub\u003e, ν(NP)\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003e813.9 (2)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e949.4 (17)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e943.2 (4)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e\u0026minus;170.1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e\u0026minus;157.9\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e\u0026minus;4.0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e\u0026minus;2.5\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003eν\u003csub\u003e5\u003c/sub\u003e, ρ(NH\u003csub\u003e2\u003c/sub\u003e)\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003e170.3 (110)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e723.0 (177)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e739.8 (100)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e\u0026minus;74.5\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e\u0026minus;74.5\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e\u0026minus;4.7\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e\u0026minus;3.8\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003eν\u003csub\u003e6\u003c/sub\u003e, ω(NH\u003csub\u003e2\u003c/sub\u003e)\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003c/tbody\u003e\u003c/colgroup\u003e\u003c/table\u003e\u003c/div\u003e\u003c/p\u003e\u003cp\u003e[a] Calculated IR frequencies (\u0026gt;\u0026thinsp;400 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e) and intensities (km mol\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e, in parentheses) at the CCSD(T)-F12B/VTZ-F12 level of theory using configuration-selective vibrational configuration interaction theory (VCI) for H\u003csub\u003e2\u003c/sub\u003eNP. [b] Observed band position (cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e) for the strongest matrix site in N\u003csub\u003e2\u003c/sub\u003e-matrix at 10 K. [c] Calculated and observed D-isotopic shifts for singlet H(D)NP. [d] Calculated and observed \u003csup\u003e\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003eN-isotopic shifts for singlet H\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e15\u003c/sup\u003eNP. [e] Assignment of the vibrational modes. [f] Not observed due to overlap with the IR band of H\u003csub\u003e2\u003c/sub\u003eO.\u003c/p\u003e\n\u003ch3\u003ePhotoreactions of HNP\u003c/h3\u003e\n\u003cp\u003eIn an attempt to generate the least stable isomer H\u003csub\u003e2\u003c/sub\u003ePN on the potential energy surface of the [2H, N, P] system, photoexcitation of the matrix-isolated HPNH was carried out by using short-wavelength irradiations at 254 and 193 nm. However, no isomerization but dehydrogenation to yield PN was observed. Additionally, chemical trapping reaction was performed by photolysis of HPNH at 395 nm in solid CO ice at 10 K. The corresponding IR difference spectrum (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eA) shows exclusive formation of H\u003csub\u003e2\u003c/sub\u003eNPCO,\u003csup\u003e\u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e47\u003c/span\u003e\u003c/sup\u003e implying first formation of H\u003csub\u003e2\u003c/sub\u003eNP from HPNH with subsequent reaction by CO. Similar photolytic CO-trapping reactions were observed before for singlet phosphinophosphinidenes\u003csup\u003e\u003cspan citationid=\"CR60\" class=\"CitationRef\"\u003e60\u003c/span\u003e\u003c/sup\u003e and triplet phenylphosphinidene.\u003csup\u003e\u003cspan citationid=\"CR61\" class=\"CitationRef\"\u003e61\u003c/span\u003e,\u003cspan citationid=\"CR62\" class=\"CitationRef\"\u003e62\u003c/span\u003e\u003c/sup\u003e Absence of the CO-trapping product of the putative intermediate H\u003csub\u003e2\u003c/sub\u003ePN (+\u0026thinsp;CO \u0026rarr; H\u003csub\u003e2\u003c/sub\u003ePNCO) suggests that it is not involved in the photochemistry of HPNH, since similar CO-trapping reaction was observed before for the fluorine derivative F\u003csub\u003e2\u003c/sub\u003ePN (+\u0026thinsp;CO \u0026rarr; F\u003csub\u003e2\u003c/sub\u003ePNCO).\u003csup\u003e\u003cspan citationid=\"CR59\" class=\"CitationRef\"\u003e59\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eTo further explore the reactivity of H\u003csub\u003e2\u003c/sub\u003eNP, its oxidation by molecular oxygen was studied in an O\u003csub\u003e2\u003c/sub\u003e-doped N\u003csub\u003e2\u003c/sub\u003e-matrix (5%) at 10 K. Upon 395 nm irradiation, a new species forms with a group of IR bands at 3529.6, 3423.4, 1540.0, 1434.7, 1191.7, and 909.8 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eB). The two bands at 1434.7 and 1191.7 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e exhibit large \u003csup\u003e\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e\u003c/sup\u003eO-isotopic shifts of \u0026minus;\u0026thinsp;40.2 and \u0026minus;\u0026thinsp;37.6 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e, supporting their assignment to the asymmetric and symmetric OPO stretching vibration modes in the oxidation product H\u003csub\u003e2\u003c/sub\u003eNPO\u003csub\u003e2\u003c/sub\u003e (\u0026larr; H\u003csub\u003e2\u003c/sub\u003eNP\u0026thinsp;+\u0026thinsp;O\u003csub\u003e2\u003c/sub\u003e). The two stretching modes are close to the same modes in other dioxophosphoranes CH\u003csub\u003e3\u003c/sub\u003ePO\u003csub\u003e2\u003c/sub\u003e (1404.3 and 1159.6 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e, N\u003csub\u003e2\u003c/sub\u003e-matrix)\u003csup\u003e\u003cspan citationid=\"CR63\" class=\"CitationRef\"\u003e63\u003c/span\u003e\u003c/sup\u003e and PhPO\u003csub\u003e2\u003c/sub\u003e (1416 and 1170 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e, Ar-matrix).\u003csup\u003e\u003cspan citationid=\"CR61\" class=\"CitationRef\"\u003e61\u003c/span\u003e\u003c/sup\u003e The three bands at 3529.6, 3423.4, and 1540.0 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e correspond to the stretching and deformation of the NH\u003csub\u003e2\u003c/sub\u003e moiety, and they resemble the same modes in the nitrogen analogue NH\u003csub\u003e2\u003c/sub\u003eNO\u003csub\u003e2\u003c/sub\u003e (3478.0, 3359.3, and 1558.1 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e, Ar-matrix).\u003csup\u003e\u003cspan citationid=\"CR64\" class=\"CitationRef\"\u003e64\u003c/span\u003e,\u003cspan citationid=\"CR65\" class=\"CitationRef\"\u003e65\u003c/span\u003e\u003c/sup\u003e The identification of H\u003csub\u003e2\u003c/sub\u003eNPO\u003csub\u003e2\u003c/sub\u003e is further supported by the good agreement of the observed IR spectrum with the theoretical calculations (3550.4, 3439.7, 1531.3, 1417.7, and 1160.7 cm\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e, Table S2). Considering the previously observed spontaneous O\u003csub\u003e2\u003c/sub\u003e-oxidation of triplet phosphinidenes\u003csup\u003e\u003cspan citationid=\"CR61\" class=\"CitationRef\"\u003e61\u003c/span\u003e\u003c/sup\u003e and nitrenes\u003csup\u003e\u003cspan additionalcitationids=\"CR67\" citationid=\"CR66\" class=\"CitationRef\"\u003e66\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR68\" class=\"CitationRef\"\u003e68\u003c/span\u003e\u003c/sup\u003e at 30 K, the O\u003csub\u003e2\u003c/sub\u003e-doped matrix containing H\u003csub\u003e2\u003c/sub\u003eNP was annealed to 30 K to allow O\u003csub\u003e2\u003c/sub\u003e diffusion for possible thermal reaction with H\u003csub\u003e2\u003c/sub\u003eNP. However, no reaction occurs to H\u003csub\u003e2\u003c/sub\u003eNP, which is consistent with the closed-shell singlet spin nature of H\u003csub\u003e2\u003c/sub\u003eNP, since its reaction with O\u003csub\u003e2\u003c/sub\u003e is spin forbidden.\u003c/p\u003e\n\u003ch3\u003eMolecular orbitals\u003c/h3\u003e\n\u003cp\u003eThe frontier molecular orbitals of \u003cem\u003etrans\u003c/em\u003e-HPNH, \u003cem\u003ecis\u003c/em\u003e-HPNH, H₂NP, and H₂PN are depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e. In line with the double-bond characters of the PN moieties in these species, the lowest unoccupied molecular orbitals (LUMOs) correspond to the antibonding character of the PN bond. The highest occupied molecular orbitals (HOMOs) in \u003cem\u003etrans\u003c/em\u003e-HPNH, \u003cem\u003ecis\u003c/em\u003e-HPNH, and H₂NP show pronounced lone-pair character on the phosphorus atom, whereas, the HOMO in H₂PN is mainly composed by the lone-pair character on the nitrogen atom. The HOMO-1 and HOMO-2 for all the four species correspond to the π- and σ-bonding interactions of the PN moiety, respectively. In agreement with the high reactivity of these phosphorus-containing compounds, the natural bond orbital (NBO) calculations indicate significant polarization in the PN double bonds. The nitrogen atoms bear large negative partial charges of \u0026minus;\u0026thinsp;1.02 \u003cem\u003ee\u003c/em\u003e, \u0026minus;\u0026thinsp;1.04 \u003cem\u003ee\u003c/em\u003e, \u0026minus;\u0026thinsp;1.09 \u003cem\u003ee\u003c/em\u003e, and \u0026minus;\u0026thinsp;0.88 \u003cem\u003ee\u003c/em\u003e, while the phosphorus atoms carry positive charges of +\u0026thinsp;0.77 \u003cem\u003ee\u003c/em\u003e, +\u0026thinsp;0.82 \u003cem\u003ee\u003c/em\u003e, +\u0026thinsp;0.33 \u003cem\u003ee\u003c/em\u003e, and +\u0026thinsp;0.98 \u003cem\u003ee\u003c/em\u003e for \u003cem\u003etrans\u003c/em\u003e-HPNH, \u003cem\u003ecis\u003c/em\u003e-HPNH, H\u003csub\u003e2\u003c/sub\u003eNP, and H\u003csub\u003e2\u003c/sub\u003ePN, respectively.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e"},{"header":"Conclusion","content":"\u003cp\u003eIn conclusion, the prototype phosphorus-nitrogen compound HPNH in the \u003cem\u003ecis\u003c/em\u003e and \u003cem\u003etrans\u003c/em\u003e conformations has been generated in the gas phase and characterized with IR and UV-vis spectroscopy in N\u003csub\u003e2\u003c/sub\u003e-matrices at 10 K. In addition to the photo-induced \u003cem\u003ecis\u003c/em\u003e ⇄ \u003cem\u003etrans\u003c/em\u003e conformational interconversion, the photochemistry of HPNH at 395 nm in the matrix reveals isomerization to the long sought-after aminophosphinidene H\u003csub\u003e2\u003c/sub\u003eNP in the singlet ground state. The first time observation of these prototype species complements the fundamental knowledge of phosphorus-nitrogen compounds. Considering the previously proposed possible involvement of the [2H, N, P] isomers in the astrochemical network of the important phosphorus-bearing species PN in the interstellar medium (ISM), the disclosed photoreactivity of these isomers including the reactions of H\u003csub\u003e2\u003c/sub\u003eNP with CO and O\u003csub\u003e2\u003c/sub\u003e could be of interest in understanding the interstellar phosphorus chemistry.\u003c/p\u003e"},{"header":"Methods","content":"\u003cp\u003e\u003cb\u003eSample preparation.\u003c/b\u003e Di-\u003cem\u003etert\u003c/em\u003e-butylaminophosphane ((\u003cem\u003et\u003c/em\u003e-Bu)\u003csub\u003e2\u003c/sub\u003ePNH\u003csub\u003e2\u003c/sub\u003e) was synthesized by reaction of (\u003cem\u003et-\u003c/em\u003eBu)\u003csub\u003e2\u003c/sub\u003ePCl (97%, Adamas) with NH\u003csub\u003e3\u003c/sub\u003e (99%, Wetry) according to the published protocol.\u003csup\u003e\u003cspan citationid=\"CR69\" class=\"CitationRef\"\u003e69\u003c/span\u003e\u003c/sup\u003e The purity of (\u003cem\u003et\u003c/em\u003e-Bu)\u003csub\u003e2\u003c/sub\u003ePNH\u003csub\u003e2\u003c/sub\u003e was checked with \u003csup\u003e\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e\u003c/sup\u003eP NMR spectroscopy (Fig. S9). For the \u003csup\u003e\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003eN- and D-labeled (\u003cem\u003et\u003c/em\u003e-Bu)\u003csub\u003e2\u003c/sub\u003ePNH\u003csub\u003e2\u003c/sub\u003e, \u003csup\u003e\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003eNH\u003csub\u003e3\u003c/sub\u003e and ND\u003csub\u003e3\u003c/sub\u003e gases were used. \u003csup\u003e\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003eNH\u003csub\u003e3\u003c/sub\u003e was synthesized by heating the mixture of Ca(OH)\u003csub\u003e2\u003c/sub\u003e and NH\u003csub\u003e4\u003c/sub\u003eCl (99% atom \u003csup\u003e\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003eN, Cambridge) with an alcohol burner, and ND\u003csub\u003e3\u003c/sub\u003e is commercially available.\u003c/p\u003e\u003cp\u003e\u003cb\u003eMatrix‑isolation IR and UV-vis spectroscopy.\u003c/b\u003e The setups for matrix-isolation experiments were described before.\u003csup\u003e[49]\u003c/sup\u003e Briefly, matrix-isolation IR spectra were recorded at resolution of 0.5 cm\u003csup\u003e− 1\u003c/sup\u003e on an FT-IR spectrometer (Bruker 70 V). To prepare the matrix, gaseous samples were mixed by passing a flow of matrix gas (N\u003csub\u003e2\u003c/sub\u003e) through a cold U-trap (–20°C) containing ca. 20 mg of freshly synthesized (\u003cem\u003et-\u003c/em\u003eBu)\u003csub\u003e2\u003c/sub\u003ePNH\u003csub\u003e2\u003c/sub\u003e. Then the mixture of (\u003cem\u003et-\u003c/em\u003eBu)\u003csub\u003e2\u003c/sub\u003ePNH\u003csub\u003e2\u003c/sub\u003e vapor/N\u003csub\u003e2\u003c/sub\u003e (~ 1:1000 estimated) was passed through an Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e tube furnace (o.d. 2.0 mm, i.d. 1.0 mm), which can be heated over a length of ca. 30 mm by a tantalum wire (resistance 2.9 Ω, voltage 10.0 V, and current 3.50 A). The resulting pyrolysis products were deposited (2 mmol h\u003csup\u003e− 1\u003c/sup\u003e) onto the gold-plated copper block matrix support (10 K) in a high vacuum (∼10\u003csup\u003e− 6\u003c/sup\u003e Pa) using a closed-cycle helium cryostat (Sumitomo Heavy Industries, SRDK-408D2-F50H) inside the chamber. Matrix-isolation UV-vis spectra were recorded on a PerkinElmer Lambda 850 + spectrometer (190–600 nm, scanning speed of 1 nm s\u003csup\u003e− 1\u003c/sup\u003e). The high-vacuum flash pyrolysis products were deposited onto a CaF\u003csub\u003e2\u003c/sub\u003e matrix support (10 K) for the measurements. Photolysis experiments were performed by using UV flashlight LEDs including 410 nm (10 W), 395 nm (15 W), 365 nm (15 W), and 310 nm (15 W).\u003c/p\u003e\u003cp\u003e\u003cb\u003eQuantum chemistry calculation.\u003c/b\u003e Structures and IR frequencies for stationary points and transition states of the [2H, P, N] system were initially calculated at the DSD-PBEP86/aug-cc-pVTZ level of theory.\u003csup\u003e\u003cspan citationid=\"CR70\" class=\"CitationRef\"\u003e70\u003c/span\u003e\u003c/sup\u003e For the calculations on the decomposition of (\u003cem\u003et-\u003c/em\u003eBu)\u003csub\u003e2\u003c/sub\u003ePNH\u003csub\u003e2\u003c/sub\u003e, the B3LYP/6-311 + + G(3df,3pd)\u003csup\u003e71,72\u003c/sup\u003e method was used. Local minima were confirmed by vibrational frequency analysis, and the transition states were ascertained with additional intrinsic reaction coordinate (IRC) calculations.\u003csup\u003e\u003cspan citationid=\"CR73\" class=\"CitationRef\"\u003e73\u003c/span\u003e\u003c/sup\u003e These calculations were performed using the Gaussian 16 software package.\u003csup\u003e\u003cspan citationid=\"CR74\" class=\"CitationRef\"\u003e74\u003c/span\u003e\u003c/sup\u003e Time-dependent (TD)\u003csup\u003e\u003cspan citationid=\"CR75\" class=\"CitationRef\"\u003e75\u003c/span\u003e\u003c/sup\u003e calculations at the DSD-PBEP86/aug-cc-pVTZ level was performed for the prediction of UV-vis transitions energies. Single-point energies were corrected at the CCSD(T)/CBS level.\u003csup\u003e\u003cspan citationid=\"CR76\" class=\"CitationRef\"\u003e76\u003c/span\u003e,\u003cspan citationid=\"CR77\" class=\"CitationRef\"\u003e77\u003c/span\u003e\u003c/sup\u003e These calculations were performed using the ORCA 5.0 software package.\u003csup\u003e\u003cspan citationid=\"CR78\" class=\"CitationRef\"\u003e78\u003c/span\u003e\u003c/sup\u003e Further vibrational frequency calculations were carried out at the CCSD(T)-F12B/VTZ-F12\u003csup\u003e79,80\u003c/sup\u003e level using configuration-selective vibrational configuration interaction (VCI)\u003csup\u003e\u003cspan citationid=\"CR52\" class=\"CitationRef\"\u003e52\u003c/span\u003e\u003c/sup\u003e theory with Molpro 2019 package.\u003csup\u003e\u003cspan citationid=\"CR81\" class=\"CitationRef\"\u003e81\u003c/span\u003e\u003c/sup\u003e The NRT calculations were carried out with the NBO 6.0.\u003csup\u003e\u003cspan citationid=\"CR82\" class=\"CitationRef\"\u003e82\u003c/span\u003e\u003c/sup\u003e The molecular orbital graphs are rendered by the VMD 1.9.3 program.\u003csup\u003e\u003cspan citationid=\"CR83\" class=\"CitationRef\"\u003e83\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eData availability\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eIR spectra for the photochemistry of HPNH in matrices, \u003csup\u003e31\u003c/sup\u003eP NMR spectrum for (\u003cem\u003et\u003c/em\u003e-Bu)\u003csub\u003e2\u003c/sub\u003ePNH\u003csub\u003e2\u003c/sub\u003e, quantum calculation results, and the atomic coordinates for all discussed species are provided in the Supplementary Information.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAcknowledgement\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis work is supported by the National Natural Science Foundation of China (22025301, U23B20163, 22206027, and 22473030).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor contributions\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eX.Z. conceived project and designed the experiments. J.J. performed the synthesis and spectroscopic measurements. L.W. and Y.G. also contributed to the spectroscopic measurements and analysis of the spectral data. J.J, Y.G., L.H. and G.R. carried out the quantum chemical calculations. L.W., J.J., and X.Z. discussed the results and drafted the manuscript. All authors commented on the manuscript.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompeting interests\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare no competing interests.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAdditional information\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eSupplementary information\u003c/strong\u003e The online version contains supplementary material available at https://doi.org/\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCorrespondence\u003c/strong\u003e and requests for materials should be addressed to Lina Wang and Xiaoqing Zeng.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eFischer, R. C. \u0026amp; Power, P. P. \u0026pi;-Bonding and the lone pair effect in multiple bonds involving heavier main group elements: Developments in the new millennium. \u003cem\u003eChem. 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Graph.\u003c/em\u003e \u003cstrong\u003e14\u003c/strong\u003e, 33\u0026minus;38 (1996).\u003c/li\u003e\n\u003c/ol\u003e"},{"header":"Schemes","content":"\u003cp\u003eSchemes 1 and 2 are available in the Supplementary Files section.\u003c/p\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"nature-portfolio","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"","title":"Nature Portfolio","twitterHandle":"","acdcEnabled":false,"dfaEnabled":false,"editorialSystem":"ejp","reportingPortfolio":"","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-7398545/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-7398545/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe simplest iminophosphane HPNH and aminophosphinidene H\u003csub\u003e2\u003c/sub\u003eNP are prototype molecules bearing phosphorus-nitrogen multiple bonds; however, both species remain hitherto unobserved. Here, we report the first time synthesis and characterization of HPNH and H\u003csub\u003e2\u003c/sub\u003eNP. Specifically, the \u003cem\u003ecis\u003c/em\u003e and \u003cem\u003etrans\u003c/em\u003e conformers of HPNH have been prepared in the gas phase by high-vacuum flash pyrolysis of di-\u003cem\u003etert\u003c/em\u003e-butylphosphanamine at ca. 950 K and subsequently isolated in solid N\u003csub\u003e2\u003c/sub\u003e-matrices at 10 K for the characterization by matrix-isolation IR (with D- and \u003csup\u003e\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003eN-isotope labeling) and UV-vis spectroscopy. In addition to the photo-induced conformational interconversion between \u003cem\u003etrans\u003c/em\u003e-HPNH and \u003cem\u003ecis\u003c/em\u003e-HPNH, their photoisomerization with H\u003csub\u003e2\u003c/sub\u003eNP has also been observed in the cryogenic matrices. In accordance with the very recently predicted lower energy of the singlet state than the triplet state by 0.2 kcal mol\u003csup\u003e\u0026ndash;\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e for H\u003csub\u003e2\u003c/sub\u003eNP, its experimental IR spectrum shows good agreement with the calculations for the singlet state at the CCSD(T)-F12B/VTZ-F12 level using configuration-selective vibrational configuration interaction (VCI) theory. Upon photoexciation at 395 nm, the matrix-isolated H\u003csub\u003e2\u003c/sub\u003eNP reacts with CO and O\u003csub\u003e2\u003c/sub\u003e to yield H\u003csub\u003e2\u003c/sub\u003eNPCO and H\u003csub\u003e2\u003c/sub\u003eNPO\u003csub\u003e2\u003c/sub\u003e as the trapping and oxidation products, respectively.\u003c/p\u003e","manuscriptTitle":"The Simplest Iminophosphane HPNH and Its Photoisomerization to Aminophosphinidene H2NP","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-08-26 11:03:23","doi":"10.21203/rs.3.rs-7398545/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"nature-communications","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"NCOMMS","sideBox":"Learn more about [Nature Communications](http://www.nature.com/ncomms/)","snPcode":"","submissionUrl":"https://mts-ncomms.nature.com/","title":"Nature Communications","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Nature Communications","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"2e01180e-7f7b-47f1-81cb-d37ace3664a8","owner":[],"postedDate":"August 26th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":53720849,"name":"Physical sciences/Chemistry/Inorganic chemistry/Chemical bonding"},{"id":53720850,"name":"Physical sciences/Chemistry/Physical chemistry/Chemical physics"}],"tags":[],"updatedAt":"2026-02-17T08:08:05+00:00","versionOfRecord":{"articleIdentity":"rs-7398545","link":"https://doi.org/10.1038/s41467-026-68391-7","journal":{"identity":"nature-communications","isVorOnly":false,"title":"Nature Communications"},"publishedOn":"2026-01-22 05:00:00","publishedOnDateReadable":"January 22nd, 2026"},"versionCreatedAt":"2025-08-26 11:03:23","video":"","vorDoi":"10.1038/s41467-026-68391-7","vorDoiUrl":"https://doi.org/10.1038/s41467-026-68391-7","workflowStages":[]},"version":"v1","identity":"rs-7398545","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-7398545","identity":"rs-7398545","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}