Carbon–arsine and carbon–antimony bonds activation of AsPh3 and SbPh3 at dimanganese and dirhenium centers in bimetallic clusters

Carbon–arsine and carbon–antimony bonds activation of AsPh3 and SbPh3 at dimanganese and dirhenium centers in bimetallic clusters | 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 Research Article Carbon–arsine and carbon–antimony bonds activation of AsPh3 and SbPh3 at dimanganese and dirhenium centers in bimetallic clusters Md. Jobayer Ahmed, Md. Sohag Hasan, Md. Atikul Islam, Md. Enamul Haque, and 5 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7815224/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted 11 You are reading this latest preprint version Abstract The reactivity of [M 2 (CO) 8 (NCMe) 2 ] (Mn, Re) with EPh 3 (E = As, Sb) has been illustrated. Bimetallic manganese-arsenic complexes, [Mn 2 (CO) 7 (µ-AsPh 2 )(AsPh 3 )(µ-H)] ( 1 ) and [Mn 2 (CO) 8 (µ-AsPh 2 ) 2 ] ( 2 ) were produced from the reaction of [Mn₂(CO) 8 (NCMe) 2 ] with AsPh 3 in refluxing toluene. The controlled experiment shows that 1 is a precursor of 2 . It can be speculated that activation of one phenyl group from the coordinated AsPh 3 of 1 formed a second bridging (µ-AsPh 2 ) ligand. The cleaved phenyl group most probably combines with the departed edge-bridging hydride to produce benzene as a byproduct. In contrast, a similar reaction with SbPh 3 gave [Mn 2 (CO) 8 (µ-SbPh 2 ) 2 ] ( 3 ) as the sole product. On the other hand, identical reaction of [Re₂(CO) 8 (NCMe) 2 ] and AsPh 3 resulted a new type of rhenium-arsenic bimetallic complex [Re 2 (CO) 5 (σ-Ph)(µ-MeCO 2 )(µ-AsPh 2 ) 2 ] ( 5 ) along with two previously reported hydride compounds [Re 2 (CO) 6 (AsPh 3 ) 2 (µ-AsPh 2 )(µ-H)] ( 4 ) and [Re(CO) 4 (AsPh 3 )H] ( 6 ). The coordination mechanism of the µ-MeCO 2 ligand is unknown, as the source of MeCO 2 is unpredictable. However, we have observed similar incidents in Os 3 -dithiocarbamate chemistry. At this end, we believe C–CN bond activation, followed by a coupling of a CO 2 molecule from the atm osphe re, produces MeCO 2, which is a four-electron donor ligand. Molecular structures of the new products 1 , 3 , and 5 were unambiguously established through spectroscopic data and single-crystal X-ray diffraction studies. The bonding in these new complexes has been examined by density functional theory (DFT) calculations. Bimetallic complexes As–C and Sb–C bond activations Diphenyl arsenide X-ray structure Figures Figure 1 Figure 2 Figure 3 1. Introduction Bimetallic complexes incorporating manganese/rhenium and heavier group 15 elements (As, Sb) have garnered significant interest due to their intriguing structural, electronic, and potential catalytic properties. The presence of heavier p-block elements in transition metal frameworks can significantly alter their electronic environments, impacting their reactivity and possible applications in catalysis, small-molecule activation, and materials chemistry [ 1 , 2 ]. To achieve this goal, the chemistry of manganese/rhenium carbonyl compounds has been explored due to their ability to form diverse structural motifs and their potential catalytic applications [ 3 – 9 ]. The incorporation of heavier group-15 elements, such as arsine and antimony, into transition metal frameworks often leads to interesting bonding interactions, stabilizing metal-metal bonds and enabling ligand-based reactivity [ 10 – 12 ]. Previous studies have demonstrated that phosphine-supported manganese/rhenium clusters can exhibit enhanced reactivity toward antimony and structural diversity, depending on the nature of the phosphine donor and the electronic environment imparted by the heavier p-block elements [ 13 , 14 ]. As weaker ligands, arsine and stibine donors have received considerably less attention in coordination chemistry compared to phosphine ligands. However, several groups have reported manganese/rhenium-arsenic/antimony bonded complexes, highlighting the diversity of their bonding modes (Chart 1 ) and reactivity [ 15 , 16 ]. In the early 1960s, the first bimetallic manganese-arsenic carbonyl complex [Mn 2 (CO) 8 (SbPh 2 ) 2 ] was reported by Lambert from reaction of with Mn 2 (CO) 10 , at 139 o C and the product was identified by IR, TGA and magnetic moment measurement [ 17 ], while the first stibine-substituted bimetallic Mn 2 and Re 2 compounds [Mn 2 (CO) 9 (SbPh 3 )], [Mn 2 (CO) 8 (SbPh 3 ) 2 ], and [Re 2 (CO) 9 (SbPh 3 )] were reported in late 1990s by Levason et al. from the photochemical reactions between [M 2 (CO) 10 ] (M = Mn, Re) and SbPh 3 [ 18 ]; the mono-substituted compounds being structurally characterized. Later in 2011, Miyamoto and coworkers reported [Mn 2 (CO) 8 (µ-AsPh 2 ) 2 ] by the reaction of Mn(CO) 5 Br with excess AsPh 3 in refluxing toluene, crystallized it by slow evaporation of solvent, and characterized it by single crystal X-ray analysis [ 5 ]. Rhenium-antimony complexes have been reported to exhibit unusual reactivities, which are different from those of Mn–Sb complexes. For example, Adams and co-workers [ 19 ] communicated the synthesis and characterization of an interesting example of a Re 2 Sb compound [Re 2 (CO) 8 (σ-C 6 H 5 )(µ-SbPh 2 )(SbPh 3 )] (70% yield) from the reaction of [Re 2 (CO) 8 {µ,η 2 -C(H) = C(H)Bu}(µ-H] with SbPh 3 at 68°C which they also obtained from the photochemical reaction of Re 2 (CO) 10 with SbPh 3 together with [Re(CO) 4 (SbPh 3 )H], [Re(CO) 4 (Ph)(SbPh 3 )] and fac-[Re(CO) 3 (Ph)(SbPh 3 ) 2 ], all in low yields. They also reported that [Re 2 (CO) 8 (σ-Ph)(µ-SbPh 2 )(SbPh 3 )] reacts with molecular hydrogen to give the dirhenium-hydride complexes [Re 2 (CO) 8 (µ-SbPh 2 )(µ-H)] and [Re 2 (CO) 7 (µ-SbPh 2 )(SbPh 3 )(µ-H)]. In contrast, the related Mn–Sb and Mn–As chemistry has not yet been developed, most likely due to the instability of the products, which precludes their isolation. Over the last few years, we have focused our attention on the synthesis and reactivity studies of transition metal carbonyl clusters with SbPh 3 and AsPh 3 ligands [ 20 – 24 ]. Recently, we have reported the reactivity of several high-valent Ru/Os carbonyl clusters with SbPh 3 and AsPh 3 ligands, affording a range of polynuclear carbonyl clusters bearing arsine/stibine, arsenide/stibene, and arsinidene/stibinidene ligands [ 20 – 22 ]. In related works, our group has also demonstrated the chemistry of low-valent monoacetonitrile-substituted rhenium complexes, [Re 2 (CO) 9 (NCMe)] and [Re 3 (CO) 11 (NCMe)(µ-H) 3 ], towards SbPh₃ [ 23 ] and AsPh₃ [ 24 ], resulting in the formation of a series of mono–, di–, and trinuclear complexes by cleavage of Sb–C and As–C bonds. In 2009, we reported that distinctly different products were obtained from the reactions [M 2 (CO) 8 (NCMe) 2 ] (M = Re, Mn) with tris(2-thienyl)phosphine compared to those obtained from the reactions with the parent carbonyls [M 2 (CO) 10 ] (M = Re, Mn) [ 25 ]. Similar to the above studies, the chemistry of thiosaccharine with rhenium is often very different from that of manganese. [ 26 , 27 ] However, no report is available in the literature on the reactivity of [M 2 (CO) 8 (NCMe) 2 ] (M = Re, Mn) with EPh 3 (E = As, Sb, Bi) ligands. Herein, we report a comparative study of the reactivity of these bis(acetonitrile) compounds towards AsPh 3 and SbPh 3 . We observed that different kinds of products were formed depending on metal carbonyl precursors and the ligands employed. 2. Experimental section All reactions were carried out under an atmosphere of dry nitrogen using the standard Schlenk technique unless otherwise noted. Reagent-grade solvents were dried using appropriate drying agents and distilled before use by standard methods. Infrared spectra were recorded with a Shimadzu IR Prestige-21 spectrophotometer. 1 H NMR spectra of the complexes were recorded using a Bruker-DPX 400 MHz spectrometer. The starting compounds [Mn 2 (CO) 8 (NCMe) 2 ] and [Re 2 (CO) 8 (NCMe) 2 ] were prepared according to the published procedures [ 28 , 29 ]. The ligands AsPh 3 and SbPh 3 were purchased from Sigma-Aldrich and used without further purification. Combustion microanalyses were done by the Microanalytical Laboratories of the Wazed Miah Science Research Centre at Jahangirnagar University. Chromatographic separations were performed in the air on TLC plates coated with 0.25 mm of silica gel (HF254-type 60, E. Merck, Germany). 2.1 Reaction of [Mn 2 (CO) 8 (NCMe) 2 ] with AsPh 3 A toluene solution (15 mL) of [Mn 2 (CO) 8 (NCMe) 2 ] (100 mg, 0.24 mmol) and AsPh 3 (147 mg, 0.48 mmol) were heated to reflux for 1.5 h. After cooling to room temperature, the solvent was removed under reduced pressure, and the residue was dissolved in a minimum volume of CH 2 Cl 2 and separated by preparative TLC on silica gel. Elution with cyclohexane/dichloromethane (9:1 v/v) afforded two minor and one major band. The minor bands afforded [Mn 2 (CO) 10 ] (4.8 mg, 5%) and unreacted [Mn 2 (CO) 8 (NCMe) 2 ] (6 mg, 6%), in order of elution. Recrystallization of the major band from n-hexane/dichloromethane at _ 4 o C gave a mixture of red and pale-yellow crystals, which were separated mechanically. The red crystals furnished the new complex [Mn 2 (CO) 7 (µ-AsPh 2 )(µ-H)(AsPh 3 )] ( 1 ) (40.5 mg, 20%) while the pale-yellow crystals afforded the known [ 5 ] compound [Mn 2 (CO) 8 (µ-AsPh 2 ) 2 ] ( 2 ) (28.6 mg, 15%). Analytical and spectroscopic data for 1 : Anal. Calcd. for C 37 H 26 As 2 Mn 2 O 7 : C, 52.76, H, 3.11. Found C, 52.97, H, 3.25. IR (ν(CO), CH 2 Cl 2 ): 2048 s, 1989 vs, 1942 s, 1956 s cm –1 . 1 H NMR (CDCl 3 ): δ 7.86 (d, J = 5.6 Hz, 4H), 7.67 (d, J = 5.6 Hz, 1H), 7.53 (m, 6H), 7.45 (m, 8H), 7.32 (m, (d, J = 5.6 Hz, 6H), − 16.37(s, 1H). 2.2 Conversion of 1 to 2 A toluene solution (10 mL) of 1 (10 mg, 0.012 mmol) was heated to reflux for 1.5 h. The solvent was removed under reduced pressure, and the residue was chromatographed by preparative TLC on silica gel. Elution with cyclohexane/dichloromethane (9:1, v/v) developed two bands. The first band gave 1 (trace) while the second band afforded 2 (5.6 mg, 60%). 2.3 Reaction of [Mn 2 (CO) 8 (NCMe) 2 ] with SbPh 3 A mixture of [Mn 2 (CO) 8 (NCMe) 2 ] (50 mg, 0.12 mmol) and SbPh 3 (82 mg, 0.23 mmol) in toluene was stirred at 80 ̊C for 1 h, during which time the colour changed from yellow to pale yellow. The solvent was removed under reduced pressure and the residue was chromatographed by TLC on silica gel. Elution with cyclohexane/dichloromethane (7:3, v/v) developed two bands. The second band yielded [Mn 2 (CO) 8 (µ-SbPh 2 ) 2 ] ( 3 ) (26.6 mg, 25%) as yellow crystals after recrystallization from n-hexane/dichloromethane at _ 4 o C. The other band was too small to characterize. Analytical and spectroscopic data for 3 : Anal. Calcd. for C 32 H 20 O 8 Mn 2 Sb 2 : C, 43.39, H, 2.28. Found: C, 43.57, H, 2.39%. IR (ν(CO), CH 2 Cl 2 ): 2062 s, 2035 w, 1973 vs, 1950 s cm –1 . 1 H NMR (CDCl 3 ): δ 8.25 (s, 4H), 7.84 (s, 2H), 7.58 (s, 7H), 7.46 (s, 1H), 7.40 (s, 4H), 7.22 (s, 1H). 2.4 Reaction of [Re 2 (CO) 8 (NCMe) 2 ] with AsPh 3 To a solution of [Re 2 (CO) 8 (NCMe) 2 ] (50 mg, 0.074 mmol) in toluene (20 mL) was added solid AsPh 3 (49 mg, 0.160 mmol), and the solution was heated to reflux at 110 o C for 3 h. The solvent was removed under reduced pressure, and the residue was redissolved in a minimum volume of CH 2 Cl 2 and applied to silica gel TLC plates. Elution with cyclohexane/dichloromethane (9:1, v/v) developed three bands which afforded, in order of elution, [(µ-H)Re 2 (CO) 6 (AsPh 3 ) 2 (µ-AsPh 2 )] ( 4 ) (10 mg, 10%) as pale yellow crystals, [Re 2 (CO) 5 (σ-Ph)(µ-MeCO 2 )(µ-AsPh 2 ) 2 ] ( 5 ) (4.1 mg, 2%) as orange crystals and [HRe(CO) 4 (AsPh 3 )] ( 6 ) (9.8 mg, 11%) as orange crystals after recrystallization from n-hexane/dichloromethane at _ 4 o C. Compounds 4 and 6 are previously reported [ 38 ]. Analytical and spectroscopic data for 5 : Anal. Calcd. for C 37 H 28 O 7 Re 2 As 2 : C, 40.15; H, 2.55. Found C, 40.05; H, 2.67%. IR (ν(CO), CH 2 Cl 2 ): 2033 s, 2004 s, 1962 s, 1938 s, 1890 m cm − 1 . 1 H NMR (CDCl 3 ): δ 7.95 (d, J = 8 Hz, 2H), 7.79 (m, 2H), 7.63 (m, 3H), 7.56 (m, 3H), 7.44 (m, 7H), 7.40 (m, 3H), 7.18 (m, 3H), 7.12 m, 2H), 3.56 (s, 3H). 2.5 X-ray structure determination Single crystals of complexes 1 , 2 , 3 , and 5 suitable for X-ray diffraction studies were obtained by slow diffusion of n-hexane into a CH 2 Cl 2 solution of each compound at 4 o C. Each suitable single crystal was mounted on a XtaLAB Synergy, Dualflex, HyPix, diffractometer using a Nylon loop and Paratone oil using Mo-Kα radiation (λ = 0.71073). The diffraction data were collected at 149.99(10) K (for 1 ), 213 K (for 2 ), 213 K (for 3 ), and 206 K (for 5 ). Unit cell determination, data reduction, and absorption correction were done with SAINT V8.38A [ 30 ], and absorption corrections were applied using the program SADABS [ 31 ]. All the structures were solved by direct methods with the SHELXS [ 32 ] structure solution program and refined by full-matrix least-squares on F 2 using SHELXL [ 33 ] within the OLEX2 [ 34 ] graphical user interface. In all structures, non-hydrogen atoms were refined anisotropically, and the hydrogen atoms were included using a riding model. Relevant crystallographic parameters are given in Table 1 . 2.6 Computational methodology Density Functional Theory (DFT) computations were employed to optimize the geometries of compounds 1 , 2 , 3 , and 5 in the gas phase. The coordinates of the experimental structures were used to optimize geometries. All calculations were carried out using the Gaussian16 [ 35 ] software package with the M06 functional [ 36 ]. The LANLeDZ [ 37 ] basis set was adopted to describe Mn, As, and Sb atoms, while the 6-311g(d,p) basis set was used for the remaining atoms. The absence of imaginary vibrational frequencies confirmed that all optimized structures correspond to the minima. 3. Results and discussion 3.1. Reaction of [Mn 2 (CO) 8 (NCMe) 2 ] with AsPh 3 The reaction of [Mn 2 (CO) 8 (NCMe) 2 ] with AsPh 3 in refluxing toluene afforded red crystals of [(µ-H)(Mn 2 (CO) 7 (µ-AsPh 2 )(AsPh 3 )] ( 1 ) (20% yield) and pale yellow crystals of a previously reported compound [Mn 2 (CO) 8 (µ-AsPh 2 ) 2 ] ( 2 ) (15% yield) (Scheme 1 ) after chromatographic separation followed by recrystallization and manual separation of the crystals as mentioned in the experimental section. Compound 1 is a precursor of 2 . A toluene solution of 1 was converted to 2 when heated at 110 o C. Thus, compound 1 formed first, and then it converted to 2 . Both complexes were characterized by a combination of elemental analysis, ¹H NMR, and IR spectroscopy, as well as single-crystal X-ray diffraction analyses. Very recently, we reported the Re–As analogue of 1 , [Re 2 (CO) 7 (AsPh 3 )(µ-AsPh 2 )(µ-H)] [ 25 ], which is the first of its kind for Mn–As complex. The solid-state structure of 1 is shown in Fig. 1 (left), with selected bond distances and angles in Table 2 . The structure comprises a Mn 2 (µ-As) triangular system with seven terminal carbonyl groups and an equatorially coordinated terminal AsPh 3 ligand. The two manganese atoms are mutually bound and simultaneously connected by a bridging hydride and an AsPh 2 ligand. The Mn − Mn bond distance at 2.9981(5) Å is significantly longer than that in the parent carbonyl [Mn 2 (CO) 10 ] [2.90 Å] [ 38 ], which is most likely due to the bridging hydride and AsPh 2 ligands. The AsPh 2 ligand asymmetrically bridges the Mn–Mn edge [Mn(1)–As(1) 2.3365(4) and Mn(2)–As(1) 2.3769(4) Å] with the shorter distance being associated with the Mn atom, Mn(1) that contains the bulky AsPh 3 ligand. The terminal Mn(1)–As(2) bond distance of 2.4002(4) Å is significantly shorter than that observed in the analogous Re-As complex, [Re 2 (CO) 7 (AsPh 3 )(µ-AsPh 2 )(µ-H)] [2.5125(6) Å] [ 24 ] as anticipated. The shortness of the proximate Mn(1) − As(1) bond is most likely due to a weaker trans-effect caused by the AsPh 3 ligand’s different π-back bonding properties compared to CO ligands that are trans to Mn − As bonds. Similar trans-effects involving the bridging AsPh 2 , SbPh 2, and PPh 2 ligands were seen in the Re-As, Re − Sb, and Re − P bond distances in [Re 2 (CO) 7 (AsPh 3 )(µ-AsPh 2 )(µ-H)] [ 24 ], [Re 2 (CO) 7 (SbPh 3 )(µ-SbPh 2 )(µ-H)] [ 19 ], and [Re 2 (CO) 7 (PPh 3 )(µ-PPh 2 )(µ-H)] [ 39 ]. The hydride ligand was crystallographically located and refined. As expected, the 1 H NMR spectroscopy shows a high-field singlet at δ – 16.36 assigned to the bridging hydride ligand. Compound 1 is a 34-valence electron compound with one metal − metal bond and structurally as well as electronically similar to that of [(µ-H)Re 2 (CO) 7 (AsPh 3 )(µ-AsPh 2 )] [ 24 ], [Re 2 (CO) 7 (SbPh 3 )(µ-SbPh 2 )(µ-H)] [ 19 ], and [Re 2 (CO) 7 (PPh 3 )(µ-PPh 2 )(µ-H)] [ 39 ]. Scheme 2 illustrates a schematic representation of the probable mechanism of formation of 1 . We believe that structures A to C or a combination of them are probable intermediates. The source of the hydride ligand in compound 1 is most probably the solvent; similar events have also been seen previously [ 19 , 25 , 40 ]. All the Mn and As atoms are in the same plane, which made it easier to activate one Ph group from AsPh 3 to form the second µ-AsPh 2, resulting in the formation of 2 . As described earlier, compound 2 was previously crystallized from the reaction mixture by slow evaporation of toluene at room temperature [ 5 ]. Diffraction data were collected at 273 K. We have recrystallized 2 from a hexane/CH 2 Cl 2 solution at – 4 o C and collected diffraction data at low temperature (150 K). The objective was to see if it crystallized in a different space group. An ORTEP diagram of the molecular structure of 2 is represented in Fig. S1 with selected bond distances in the caption. However, the structure is very similar to that previously reported by Miyamoto et al. [ 5 ]. 2.2 Reaction of [Mn 2 (CO) 8 (NCMe) 2 ] with SbPh 3 In contrast to the AsPh 3 chemistry discussed above, a similar reaction of [Mn 2 (CO) 8 (NCMe) 2 ] and SbPh 3 in toluene at 80 o C afforded [Mn 2 (CO) 8 (µ-SbPh 2 ) 2 ] ( 3 ) as the sole product in 25% yield. We could not be successful in isolating any complex analogous to [Mn 2 (CO) 7 (AsPh 3 )(µ-AsPh 2 )(µ-H)] ( 1 ). Spectroscopic data and a single-crystal X-ray study unambiguously characterized the new product 3 . Compounds 2 and 3 are isostructural and isoelectronic. Figure 2 shows the molecular structure of 3 , and selected bond lengths and angles are collected in Table 2 . The dimer results from the two SbPh 2 ligands being in bridging coordination modes to two Mn(CO) 4 units. The Mn 2 As 2 central core is a planar rhomb with the average bond length and angles, d(Mn—Sb), ∠Sb–Mn–Sb, and ∠Mn–Sb–Mn, equal to 2.6228(12) Å, 78.07(4)°, and 101.94(4)°. While the Mn—Sb bond lengths are significantly longer than expected. The Sb–Mn–Sb and Mn–Sb–Mn bond angles are comparable to those of its As-counterpart in 2 [2.4752(5) Å, 78.993(13)° and 101.818(13)°], respectively. Analogous to 2 , the four phenyl groups are located above and below this plane. There is no metal–metal bond between the Re atoms. The Mn···Mn distance of 4.075 Å is clearly non-bonding as the Sb···Sb distance of 3.3035(17) Å. The molecule has a two-fold axis of symmetry that extends out perpendicularly to the Mn 2 Sb 2 plane. In both Mn(CO) 4 units, the two sets of four Mn–C distances are the same [1.827(5), 1.809(5), 1.849(5), 1.819(5) Å]. An interesting observation is that among the two sets of Mn(CO) 4 units, the trans Mn-C and C = O bond lengths are the same and are much closer due to the multiple bond nature of the carbonyls. The spectroscopic data for compound 3 are consistent with the XRD data. For instance, the carbonyl region of the IR spectrum shows characteristic stretching vibrations for terminal CO, while the 1 H NMR spectrum exhibits characteristic aromatic signals for the µ-SbPh 2 ligands. 2.3. Reaction of [Re 2 (CO) 8 (NCMe) 2 ] with AsPh 3 As mentioned in the introduction, we have recently investigated the reactions of [Re 2 (CO) 9 (NCMe)], and [Re 3 (CO) 11 (NCMe)(µ-H) 3 ] with AsPh₃ [ 24 ]. We have now investigated the reaction of [Re 2 (CO) 8 (NCMe) 2 ] towards AsPh₃. The objectives were to see if the bis(acetonitrile) Re compound, which exists as a 2:1 equilibrium mixture of 2,6- and 2,3-isomers (Chart 2 ) [ 28 ], would provide structurally similar products to those obtained from [Mn 2 (CO) 8 (NCMe) 2 ] and/or [Re 2 (CO) 9 (NCMe)]. The reaction of [Re 2 (CO) 8 (NCMe) 2 ] towards AsPh 3 in toluene at 80 o C followed by usual work up and chromatographic separation (detailed in experimental section) afforded the previously reported di– and mononuclear compounds [Re 2 (CO) 6 (AsPh 3 ) 2 (µ-AsPh 2 )(µ-H)] ( 4 ) [HRe(CO) 4 (AsPh 3 )] ( 6 ) in 10 and 11% yields together with a new lower yield compound [Re 2 (CO) 5 (σ-Ph)(µ-MeCO 2 )(µ-AsPh 2 ) 2 ] ( 5 ) as orange crystals. (Scheme 3 ) All attempts to increase the yield of 5 were, however, unsuccessful. The compound 5 is characterized by a combination of elemental analysis, IR, and 1 H NMR spectroscopy, as well as single-crystal X-ray diffraction analysis. The molecular structure of 5 is depicted in Fig. 3 , and the selected bond distances and angles are collected in Table 2 . The molecular structure comprises two fused triangles of Re 2 As. Unlike Mn 2 As 2 or Mn 2 Sb 2 , Re 2 As 2 is neither fully planar nor diamond. The Re–As distances are [Re(1)–As(1) 2.5381(8), Re(1)–As(2) 2.5607(8), Re(2)–As(1) 2.4405(8), Re(2)–As(2) 2.4483(9)] significantly shorter than that in [Re 2 (CO) 8 (µ-AsPh 2 ) 2 ] [2.609(l) and 2.609(l) Å] [ 5 ]. This result is due to (i) apart from the CO and AsPh 2 ligands, Re atoms are asymmetrically coordinated by a phenyl group (σ-Ph) and (ii) a bridging µ-MeCO 2 . The µ-MeCO 2 moiety is perpendicular to the Re 2 As 2 trapezium and forms an unprecedented five-membered ring by cyclometallation of Re 2 O 2 C. Although it is tough to predict how this ligand is formed, we can speculate that results from (i) one C–C bond activation happened in toluene, (ii) the phenyl group added to one of the Re atoms, and (iii) the Me group attacks a carbon center of a CO 2 ligand to make µ-MeCO 2 ligand. However, it is unclear whether the latter is formed as a result of the oxidation of a pre-bound carbonyl or via the absorption of CO 2 from the air during work-up. The binding of CO 2 to low-valent osmium clusters is surprisingly common [ 41 – 43 ]. Earlier this year, we also observed a similar fusion to form a carboxylate (µ-CO 2 ) ligand in triosmium chemistry [ 44 ]. However, the formation of a dirhenium carboxylate (Re 2 CO 2 ) system is unprecedented and interesting. The Re-O bond distances [Re(1)–O(7) 2.171(4), Re(2)–O(6) 2.167(4) Å] are similar to Os–O bond lengths [2.136(7) and 2.099(7) Å] as expected. Given that there is one Re–Re bond, then the complex is expected to have a valence electron count (VEC) of 34, which suggests that MeCO 2 acts as a 3-electron donor. The average terminal C–O bond length is 1.14 (7) Å, while the C–O bond lengths in the MeCO 2 ligand are C(6)–O(6) 1.272(7) and C(6)–O(7) 1.307(4) Å. Elongation of C(3)–O(3) and C(5)–O(5) bonds [1.155(7) and 1.157(7) Å] compared to other terminal C = O bonds [1.135 (7) Å] is the result of the trans effect µ-MeCO 2 coordination. A similar reason is true for the Re(1)–C(3) and Re(2)–C(5) interactions, where the back bonding is stronger than that of the other Re–C (from terminal CO) bonds. The spectroscopic data for compound 5 are in accord with the solid-state structure. For instance, the carbonyl region of the IR spectrum shows characteristic stretching vibrations for terminal CO, while the 1 H NMR spectrum exhibits characteristic aromatic signals for the σ-Ph and µ-AsPh 2 ligands. 2.4. DFT calculations The geometries of compounds 1 , 2 , 3 , and 5 were optimized using density functional theory (DFT) calculations. The selected bond lengths and angles obtained from X-ray diffraction (XRD) data show good agreement with the DFT optimized values. The Wiberg bond index (WBI) values provide insight into the bonding characteristics of these compounds. For compound 1 , the WBI values for Mn(1)–Mn(2), As(2)–Mn(1), and As(1)–Mn(2) are 0.7858, 0.0.7282, 0.7077, respectively which are consistent with single bonds. In contrast, the WBI values for Mn(1)–H(1), Mn(2)–H(1) and Mn(1)–Mn(2) are 0.3268, 0.3512 and 0.2365, respectively, indicating weak bonding interactions. For compound 2 , the WBI values for As(1)–Mn(1), As(1)–Mn(2), As(2)–Mn(1) and As(2)–Mn(2) are 0.6853; 0.6863, 0.6863 and 0.6853, respectively. In 3 , the WBI values for Sb(1)–Mn(1), Sb(1)A–Mn(1)A, Sb(1)A–Mn(1), and Sb(1)-Mn(1)A have WBI values are 0.7019, 0.7113, 0.7019 and 0.7113, respectively. The WBI values in 2 and 3 fall in the range of 0.0.68 ~ 0.71, confirming that these are single covalent bonds. For 5 , the WBI values for Re(1)–As(1), Re(1)–As(2), Re(2)–As(1) and Re(2)–As(2) are 0.6739, 0.6351, 0.8575, and 0.8551, respectively, all of which correspond to single covalent bonds. However, the WBI value for Re(1)–Re(2) is 0.3195, suggesting a weak bonding interaction. Summary and conclusions In summary, the bis(acetonitrile) compounds [M 2 (CO) 8 (NCMe) 2 ] (Mn, Re) are found to react with AsPh 3 and SbPh 3 to yield a variety of activated products. It has been observed that the phenyl group is readily cleaved from AsPh 3 in its reactions with Mn(CO) 8 (NCMe) 2 ] affording [Mn 2 (CO) 7 (µ-AsPh 2 )(µ-H)(AsPh 3 )] ( 1 ) and [Mn 2 (CO) 8 (µ-AsPh 2 ) 2 ] ( 2 ). Thermolysis of 1 in refluxing toluene leads to the formation of 2 . A probable reaction pathway leading to the formation of 2 has been proposed. In contrast, [Mn 2 (CO) 8 (µ-AsPh 2 ) 2 ] ( 2 ) was obtained as the only product when reacted with SbPh 3 . The manganese–manganese bond was also cleaved in these reactions. Interestingly, there is no evidence in the formation of [Mn 2 (CO) 8 (AsPh 3 ) 2 ] and [Mn 2 (CO) 8 (SbPh 3 ) 2 ], which are the likely intermediates in the formation of 1 – 3 . This is most likely As–C and Sb–C bond cleavage, which is facile at this temperature. In addition to the previously reported 4 and 6 , the σ-aryl compound [Re 2 (CO) 5 (σ-Ph)(µ-MeCO 2 )(µ-AsPh 2 ) 2 ] ( 5 ) was obtained in low yield, when [Re 2 (CO) 8 (NCMe) 2 ] was reacted with AsPh 3 in toluene at 80 o C. At this end, we believe C–CN bond activation, followed by a coupling of a CO 2 molecule from the atmosphere, produces MeCO 2, which is a four-electron donor ligand. Declarations CRediT authorship contribution statement Md. Jobayer Ahmed :Investigation,Writing-original draft , Md. Sohag Hasan :Investigation,formal analysis , Md. Atikul Islam: Investigation,formal analysis , Md. Enamul Haque :Computational analysis, Abdullah Al Mamun : Investigation,formal analysis , Joyanta K. Saha : Computational analysis, Writing, Vladimir N. Nesterov : X-ray data collection, Solving structures and editing, Shariff E. Kabir : Supervision, Project administration, Writing, Review, and editing, Jagodish C. Sarker : Supervision, Writing, Review and editing, Funding acquisition. Declaration of competing interests The authors declare no competing interests. Funding Declaration This research is funded by Jagannath University. Acknowledgements We gratefully acknowledge the support of the Bangladesh University Grants Commission (UGC) and Jagannath University. SEK also acknowledges the UGC for the award of a Professorship. JCS thanks Mr Shah Md Ariful Abed and Professor A. J. Saleh Ahmed for their help in providing some chemicals used in this work. ASSOCIATED CONTENT Supplementary material associated with this article can be found in the online version. CCDC 2493935, 2493936, 2493937 and 2404750 contain supplementary crystallographic data for 1-3 and 5 , respectively. These data may be obtained free of charge from The Cambridge Crystallographic Data Center via www.ccdc.cam.ac.uk/data_request/cif, or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223–336–033; or e-mail: [email protected] . Atomic coordinates for all optimized structures are available from VNN on request. References R. Raja, R. D. Adams, D. A. Blom, W. C. Pearl Jr., E. Gianotti, and J. M. Thomas (2009). New catalytic liquid-phase ammoxidation approach to the preparation of niacin (vitamin B3). Langmuir 25, 7200–7204. https://doi.org/10.1021/la900803a E. Gianotti, V. N. Shetti, M. Manzoli, J. A. L. Blaine, W. C. Jr. Pearl, R. D. Adams, S. Coluccia, and R. Raja (2010). 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Chem. 401 C50–C53. https://doi.org/10.1016/0022-328X(91)86240-Q Y. Chi, J. -W. Lan, S. -M. Peng, and G. -H. Lee (2001). Synthesis and characterization of tetra osmium carbonyl complexes containing a bridging CO 2 ligand. J. Clust. Sci. 12, 421–432. https://doi.org/10.1023/A:1016625218456 N. C. Bhoumik, M. N. Huda, V. N. Nesterov, G. Hogarth, S. E. Kabir, and J. C. Sarker (2025). Reactivity of labile triosmium complexes, [Os 3 (CO)10(MeCN) 2 ] and [Os 3 (CO) 10 (µ-H) 2 ] with tetraethylthiuram disulfide (disulfiram). J. Clust. Sci. 36, 34. https://doi.org/10.1007/s10876-024-02749-z Tables Tables 1 and 2 are available in the Supplementary Files section. Charts and Schemes Charts 1 and 2 are available in the Supplementary Files section Schemes 1 to 3 are available in the Supplementary Files section Additional Declarations No competing interests reported. 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16:32:08","extension":"png","order_by":21,"title":"","display":"","copyAsset":false,"role":"acdc-reference","size":93427,"visible":true,"origin":"","legend":"","description":"","filename":"Onlinefloatimage8.png","url":"https://assets-eu.researchsquare.com/files/rs-7815224/v1/e4ccf6b87a45876264146bb5.png"},{"id":95139338,"identity":"e826da1e-f699-4966-b15f-7eebb198d1e7","added_by":"auto","created_at":"2025-11-04 16:51:04","extension":"xml","order_by":22,"title":"","display":"","copyAsset":false,"role":"acdc-reference","size":157458,"visible":true,"origin":"","legend":"","description":"","filename":"46e219befe064d51954241432b8c79a81structuring.xml","url":"https://assets-eu.researchsquare.com/files/rs-7815224/v1/4a3e43ee6e9d164124a13a26.xml"},{"id":95139341,"identity":"7ee3e821-8bba-4a8a-a303-4af9574b9b82","added_by":"auto","created_at":"2025-11-04 16:51:04","extension":"html","order_by":23,"title":"","display":"","copyAsset":false,"role":"acdc-reference","size":165540,"visible":true,"origin":"","legend":"","description":"","filename":"earlyproof.html","url":"https://assets-eu.researchsquare.com/files/rs-7815224/v1/4ae4ab372fdbc6d9e211b507.html"},{"id":95139311,"identity":"82f3d955-0f5a-4b4b-b63e-a62c626b3054","added_by":"auto","created_at":"2025-11-04 16:51:03","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":347834,"visible":true,"origin":"","legend":"\u003cp\u003eMolecular structure of [(µ-H)Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e7\u003c/sub\u003e(AsPh\u003csub\u003e3\u003c/sub\u003e)(µ-AsPh\u003csub\u003e2\u003c/sub\u003e)] (\u003cstrong\u003e1\u003c/strong\u003e), showing 50% thermal ellipsoids (left) and DFT optimized structure (right). Ring hydrogen atoms are omitted for clarity.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-7815224/v1/21f53d64458df9ac897ef5b8.png"},{"id":95139315,"identity":"960f97ab-dd1b-4f16-a859-cb298caeddee","added_by":"auto","created_at":"2025-11-04 16:51:03","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":389167,"visible":true,"origin":"","legend":"\u003cp\u003eMolecular structure of [Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(µ-SbPh\u003csub\u003e2\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e] (\u003cstrong\u003e3\u003c/strong\u003e), showing 50% probability of thermal ellipsoids (left) and DFT optimized structure (right). Hydrogen atoms are omitted for clarity.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-7815224/v1/32b6e4db58214af936adac69.png"},{"id":95139313,"identity":"81c3fd5e-7f2f-4cb4-ae4a-101cb9ef32f4","added_by":"auto","created_at":"2025-11-04 16:51:03","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":373272,"visible":true,"origin":"","legend":"\u003cp\u003eMolecular structure of [Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e5\u003c/sub\u003e(σ-Ph)(µ-MeCO\u003csub\u003e2\u003c/sub\u003e)(µ-AsPh\u003csub\u003e2\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e] (\u003cstrong\u003e5\u003c/strong\u003e), showing 50% probability of thermal ellipsoids (left), and DFT optimized structure (right). Ring hydrogen atoms are omitted for clarity.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-7815224/v1/ea5a3e3863c911083cef903a.png"},{"id":95230763,"identity":"7333630f-b335-4462-9104-9d01a2d6944d","added_by":"auto","created_at":"2025-11-05 16:38:30","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2250773,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-7815224/v1/c1eab5a5-eb99-4c27-9cc3-6e930e391f3f.pdf"},{"id":95225348,"identity":"2d9b444a-2ce9-4aa7-8176-2281cc369a1d","added_by":"auto","created_at":"2025-11-05 16:24:54","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":48869,"visible":true,"origin":"","legend":"","description":"","filename":"GraphicalAbstract.docx","url":"https://assets-eu.researchsquare.com/files/rs-7815224/v1/48dbb788df3120ad306c0b92.docx"},{"id":95225962,"identity":"8dbd83ed-8870-46a5-88b4-e262549dd7db","added_by":"auto","created_at":"2025-11-05 16:25:50","extension":"pdf","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":544186,"visible":true,"origin":"","legend":"","description":"","filename":"SupplementaryESIR1.pdf","url":"https://assets-eu.researchsquare.com/files/rs-7815224/v1/55178f84d83720721c463f48.pdf"},{"id":95139320,"identity":"25846332-612a-4964-83d6-4e00bc09fde6","added_by":"auto","created_at":"2025-11-04 16:51:03","extension":"docx","order_by":3,"title":"","display":"","copyAsset":false,"role":"supplement","size":14684,"visible":true,"origin":"","legend":"","description":"","filename":"Highlights.docx","url":"https://assets-eu.researchsquare.com/files/rs-7815224/v1/0268e7db954ba1372773fd53.docx"},{"id":95139318,"identity":"1b7de8ba-4dcd-4475-bb21-2723c9508138","added_by":"auto","created_at":"2025-11-04 16:51:03","extension":"docx","order_by":4,"title":"","display":"","copyAsset":false,"role":"supplement","size":23186,"visible":true,"origin":"","legend":"","description":"","filename":"Tables.docx","url":"https://assets-eu.researchsquare.com/files/rs-7815224/v1/a777c2b70560e01292d5c127.docx"},{"id":95139322,"identity":"fdf3a79f-a86c-485e-86ec-ffab9eb4c4d5","added_by":"auto","created_at":"2025-11-04 16:51:03","extension":"docx","order_by":5,"title":"","display":"","copyAsset":false,"role":"supplement","size":180656,"visible":true,"origin":"","legend":"","description":"","filename":"ChartsandSchemes.docx","url":"https://assets-eu.researchsquare.com/files/rs-7815224/v1/01dc9bd5bdbb72ba17fe42f7.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Carbon–arsine and carbon–antimony bonds activation of AsPh3 and SbPh3 at dimanganese and dirhenium centers in bimetallic clusters","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eBimetallic complexes incorporating manganese/rhenium and heavier group 15 elements (As, Sb) have garnered significant interest due to their intriguing structural, electronic, and potential catalytic properties. The presence of heavier p-block elements in transition metal frameworks can significantly alter their electronic environments, impacting their reactivity and possible applications in catalysis, small-molecule activation, and materials chemistry [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e, \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e]. To achieve this goal, the chemistry of manganese/rhenium carbonyl compounds has been explored due to their ability to form diverse structural motifs and their potential catalytic applications [\u003cspan additionalcitationids=\"CR4 CR5 CR6 CR7 CR8\" citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e]. The incorporation of heavier group-15 elements, such as arsine and antimony, into transition metal frameworks often leads to interesting bonding interactions, stabilizing metal-metal bonds and enabling ligand-based reactivity [\u003cspan additionalcitationids=\"CR11\" citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e]. Previous studies have demonstrated that phosphine-supported manganese/rhenium clusters can exhibit enhanced reactivity toward antimony and structural diversity, depending on the nature of the phosphine donor and the electronic environment imparted by the heavier p-block elements [\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e, \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e]. As weaker ligands, arsine and stibine donors have received considerably less attention in coordination chemistry compared to phosphine ligands. However, several groups have reported manganese/rhenium-arsenic/antimony bonded complexes, highlighting the diversity of their bonding modes (Chart \u003cspan refid=\"Str1\" class=\"InternalRef\"\u003e1\u003c/span\u003e) and reactivity [\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e, \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e].\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eIn the early 1960s, the first bimetallic manganese-arsenic carbonyl complex [Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(SbPh\u003csub\u003e2\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e] was reported by Lambert from reaction of with Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e10\u003c/sub\u003e, at 139 \u003csup\u003eo\u003c/sup\u003eC and the product was identified by IR, TGA and magnetic moment measurement [\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e], while the first stibine-substituted bimetallic Mn\u003csub\u003e2\u003c/sub\u003e and Re\u003csub\u003e2\u003c/sub\u003e compounds [Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e9\u003c/sub\u003e(SbPh\u003csub\u003e3\u003c/sub\u003e)], [Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(SbPh\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e], and [Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e9\u003c/sub\u003e(SbPh\u003csub\u003e3\u003c/sub\u003e)] were reported in late 1990s by Levason et al. from the photochemical reactions between [M\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e10\u003c/sub\u003e] (M\u0026thinsp;=\u0026thinsp;Mn, Re) and SbPh\u003csub\u003e3\u003c/sub\u003e [\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e]; the mono-substituted compounds being structurally characterized. Later in 2011, Miyamoto and coworkers reported [Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(\u0026micro;-AsPh\u003csub\u003e2\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e] by the reaction of Mn(CO)\u003csub\u003e5\u003c/sub\u003eBr with excess AsPh\u003csub\u003e3\u003c/sub\u003e in refluxing toluene, crystallized it by slow evaporation of solvent, and characterized it by single crystal X-ray analysis [\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]. Rhenium-antimony complexes have been reported to exhibit unusual reactivities, which are different from those of Mn\u0026ndash;Sb complexes. For example, Adams and co-workers [\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e] communicated the synthesis and characterization of an interesting example of a Re\u003csub\u003e2\u003c/sub\u003eSb compound [Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(σ-C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e5\u003c/sub\u003e)(\u0026micro;-SbPh\u003csub\u003e2\u003c/sub\u003e)(SbPh\u003csub\u003e3\u003c/sub\u003e)] (70% yield) from the reaction of [Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e{\u0026micro;,η\u003csup\u003e2\u003c/sup\u003e-C(H)\u0026thinsp;=\u0026thinsp;C(H)Bu}(\u0026micro;-H] with SbPh\u003csub\u003e3\u003c/sub\u003e at 68\u0026deg;C which they also obtained from the photochemical reaction of Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e10\u003c/sub\u003e with SbPh\u003csub\u003e3\u003c/sub\u003e together with [Re(CO)\u003csub\u003e4\u003c/sub\u003e(SbPh\u003csub\u003e3\u003c/sub\u003e)H], [Re(CO)\u003csub\u003e4\u003c/sub\u003e(Ph)(SbPh\u003csub\u003e3\u003c/sub\u003e)] and fac-[Re(CO)\u003csub\u003e3\u003c/sub\u003e(Ph)(SbPh\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e], all in low yields. They also reported that [Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(σ-Ph)(\u0026micro;-SbPh\u003csub\u003e2\u003c/sub\u003e)(SbPh\u003csub\u003e3\u003c/sub\u003e)] reacts with molecular hydrogen to give the dirhenium-hydride complexes [Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(\u0026micro;-SbPh\u003csub\u003e2\u003c/sub\u003e)(\u0026micro;-H)] and [Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e7\u003c/sub\u003e(\u0026micro;-SbPh\u003csub\u003e2\u003c/sub\u003e)(SbPh\u003csub\u003e3\u003c/sub\u003e)(\u0026micro;-H)]. In contrast, the related Mn\u0026ndash;Sb and Mn\u0026ndash;As chemistry has not yet been developed, most likely due to the instability of the products, which precludes their isolation.\u003c/p\u003e\u003cp\u003eOver the last few years, we have focused our attention on the synthesis and reactivity studies of transition metal carbonyl clusters with SbPh\u003csub\u003e3\u003c/sub\u003e and AsPh\u003csub\u003e3\u003c/sub\u003e ligands [\u003cspan additionalcitationids=\"CR21 CR22 CR23\" citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e]. Recently, we have reported the reactivity of several high-valent Ru/Os carbonyl clusters with SbPh\u003csub\u003e3\u003c/sub\u003e and AsPh\u003csub\u003e3\u003c/sub\u003e ligands, affording a range of polynuclear carbonyl clusters bearing arsine/stibine, arsenide/stibene, and arsinidene/stibinidene ligands [\u003cspan additionalcitationids=\"CR21\" citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e]. In related works, our group has also demonstrated the chemistry of low-valent monoacetonitrile-substituted rhenium complexes, [Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e9\u003c/sub\u003e(NCMe)] and [Re\u003csub\u003e3\u003c/sub\u003e(CO)\u003csub\u003e11\u003c/sub\u003e(NCMe)(\u0026micro;-H)\u003csub\u003e3\u003c/sub\u003e], towards SbPh₃ [\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e] and AsPh₃ [\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e], resulting in the formation of a series of mono\u0026ndash;, di\u0026ndash;, and trinuclear complexes by cleavage of Sb\u0026ndash;C and As\u0026ndash;C bonds. In 2009, we reported that distinctly different products were obtained from the reactions [M\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(NCMe)\u003csub\u003e2\u003c/sub\u003e] (M\u0026thinsp;=\u0026thinsp;Re, Mn) with tris(2-thienyl)phosphine compared to those obtained from the reactions with the parent carbonyls [M\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e10\u003c/sub\u003e] (M\u0026thinsp;=\u0026thinsp;Re, Mn) [\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e]. Similar to the above studies, the chemistry of thiosaccharine with rhenium is often very different from that of manganese. [\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e, \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e] However, no report is available in the literature on the reactivity of [M\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(NCMe)\u003csub\u003e2\u003c/sub\u003e] (M\u0026thinsp;=\u0026thinsp;Re, Mn) with EPh\u003csub\u003e3\u003c/sub\u003e (E\u0026thinsp;=\u0026thinsp;As, Sb, Bi) ligands. Herein, we report a comparative study of the reactivity of these bis(acetonitrile) compounds towards AsPh\u003csub\u003e3\u003c/sub\u003e and SbPh\u003csub\u003e3\u003c/sub\u003e. We observed that different kinds of products were formed depending on metal carbonyl precursors and the ligands employed.\u003c/p\u003e"},{"header":"2. Experimental section","content":"\u003cp\u003eAll reactions were carried out under an atmosphere of dry nitrogen using the standard Schlenk technique unless otherwise noted. Reagent-grade solvents were dried using appropriate drying agents and distilled before use by standard methods. Infrared spectra were recorded with a Shimadzu IR Prestige-21 spectrophotometer. \u003csup\u003e1\u003c/sup\u003eH NMR spectra of the complexes were recorded using a Bruker-DPX 400 MHz spectrometer. The starting compounds [Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(NCMe)\u003csub\u003e2\u003c/sub\u003e] and [Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(NCMe)\u003csub\u003e2\u003c/sub\u003e] were prepared according to the published procedures [\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e, \u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e]. The ligands AsPh\u003csub\u003e3\u003c/sub\u003e and SbPh\u003csub\u003e3\u003c/sub\u003e were purchased from Sigma-Aldrich and used without further purification. Combustion microanalyses were done by the Microanalytical Laboratories of the Wazed Miah Science Research Centre at Jahangirnagar University. Chromatographic separations were performed in the air on TLC plates coated with 0.25 mm of silica gel (HF254-type 60, E. Merck, Germany).\u003c/p\u003e\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e\u003ch2\u003e2.1 Reaction of [Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(NCMe)\u003csub\u003e2\u003c/sub\u003e] with AsPh\u003csub\u003e3\u003c/sub\u003e\u003c/h2\u003e\u003cp\u003eA toluene solution (15 mL) of [Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(NCMe)\u003csub\u003e2\u003c/sub\u003e] (100 mg, 0.24 mmol) and AsPh\u003csub\u003e3\u003c/sub\u003e (147 mg, 0.48 mmol) were heated to reflux for 1.5 h. After cooling to room temperature, the solvent was removed under reduced pressure, and the residue was dissolved in a minimum volume of CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e and separated by preparative TLC on silica gel. Elution with cyclohexane/dichloromethane (9:1 v/v) afforded two minor and one major band. The minor bands afforded [Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e10\u003c/sub\u003e] (4.8 mg, 5%) and unreacted [Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(NCMe)\u003csub\u003e2\u003c/sub\u003e] (6 mg, 6%), in order of elution. Recrystallization of the major band from n-hexane/dichloromethane at \u003csup\u003e_\u003c/sup\u003e 4 \u003csup\u003eo\u003c/sup\u003eC gave a mixture of red and pale-yellow crystals, which were separated mechanically. The red crystals furnished the new complex [Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e7\u003c/sub\u003e(\u0026micro;-AsPh\u003csub\u003e2\u003c/sub\u003e)(\u0026micro;-H)(AsPh\u003csub\u003e3\u003c/sub\u003e)] (\u003cb\u003e1\u003c/b\u003e) (40.5 mg, 20%) while the pale-yellow crystals afforded the known [\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e] compound [Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(\u0026micro;-AsPh\u003csub\u003e2\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e] (\u003cb\u003e2\u003c/b\u003e) (28.6 mg, 15%).\u003c/p\u003e\u003cp\u003eAnalytical and spectroscopic data for \u003cb\u003e1\u003c/b\u003e: Anal. Calcd. for C\u003csub\u003e37\u003c/sub\u003eH\u003csub\u003e26\u003c/sub\u003eAs\u003csub\u003e2\u003c/sub\u003eMn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e7\u003c/sub\u003e: C, 52.76, H, 3.11. Found C, 52.97, H, 3.25. IR (ν(CO), CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e): 2048 s, 1989 vs, 1942 s, 1956 s cm\u003csup\u003e\u0026ndash;1\u003c/sup\u003e. \u003csup\u003e1\u003c/sup\u003eH NMR (CDCl\u003csub\u003e3\u003c/sub\u003e): δ 7.86 (d, J\u0026thinsp;=\u0026thinsp;5.6 Hz, 4H), 7.67 (d, J\u0026thinsp;=\u0026thinsp;5.6 Hz, 1H), 7.53 (m, 6H), 7.45 (m, 8H), 7.32 (m, (d, J\u0026thinsp;=\u0026thinsp;5.6 Hz, 6H), \u0026minus;\u0026thinsp;16.37(s, 1H).\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec4\" class=\"Section2\"\u003e\u003ch2\u003e2.2 Conversion of 1 to 2\u003c/h2\u003e\u003cp\u003eA toluene solution (10 mL) of 1 (10 mg, 0.012 mmol) was heated to reflux for 1.5 h. The solvent was removed under reduced pressure, and the residue was chromatographed by preparative TLC on silica gel. Elution with cyclohexane/dichloromethane (9:1, v/v) developed two bands. The first band gave \u003cb\u003e1\u003c/b\u003e (trace) while the second band afforded \u003cb\u003e2\u003c/b\u003e (5.6 mg, 60%).\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec5\" class=\"Section2\"\u003e\u003ch2\u003e2.3 Reaction of [Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(NCMe)\u003csub\u003e2\u003c/sub\u003e] with SbPh\u003csub\u003e3\u003c/sub\u003e\u003c/h2\u003e\u003cp\u003eA mixture of [Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(NCMe)\u003csub\u003e2\u003c/sub\u003e] (50 mg, 0.12 mmol) and SbPh\u003csub\u003e3\u003c/sub\u003e (82 mg, 0.23 mmol) in toluene was stirred at 80 ̊C for 1 h, during which time the colour changed from yellow to pale yellow. The solvent was removed under reduced pressure and the residue was chromatographed by TLC on silica gel. Elution with cyclohexane/dichloromethane (7:3, v/v) developed two bands. The second band yielded [Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(\u0026micro;-SbPh\u003csub\u003e2\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e] (\u003cb\u003e3\u003c/b\u003e) (26.6 mg, 25%) as yellow crystals after recrystallization from n-hexane/dichloromethane at \u003csup\u003e_\u003c/sup\u003e 4 \u003csup\u003eo\u003c/sup\u003eC. The other band was too small to characterize.\u003c/p\u003e\u003cp\u003eAnalytical and spectroscopic data for \u003cb\u003e3\u003c/b\u003e: Anal. Calcd. for C\u003csub\u003e32\u003c/sub\u003eH\u003csub\u003e20\u003c/sub\u003eO\u003csub\u003e8\u003c/sub\u003eMn\u003csub\u003e2\u003c/sub\u003eSb\u003csub\u003e2\u003c/sub\u003e: C, 43.39, H, 2.28. Found: C, 43.57, H, 2.39%. IR (ν(CO), CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e): 2062 s, 2035 w, 1973 vs, 1950 s cm\u003csup\u003e\u0026ndash;1\u003c/sup\u003e. \u003csup\u003e1\u003c/sup\u003eH NMR (CDCl\u003csub\u003e3\u003c/sub\u003e): δ 8.25 (s, 4H), 7.84 (s, 2H), 7.58 (s, 7H), 7.46 (s, 1H), 7.40 (s, 4H), 7.22 (s, 1H).\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec6\" class=\"Section2\"\u003e\u003ch2\u003e2.4 Reaction of [Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(NCMe)\u003csub\u003e2\u003c/sub\u003e] with AsPh\u003csub\u003e3\u003c/sub\u003e\u003c/h2\u003e\u003cp\u003eTo a solution of [Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(NCMe)\u003csub\u003e2\u003c/sub\u003e] (50 mg, 0.074 mmol) in toluene (20 mL) was added solid AsPh\u003csub\u003e3\u003c/sub\u003e (49 mg, 0.160 mmol), and the solution was heated to reflux at 110 \u003csup\u003eo\u003c/sup\u003eC for 3 h. The solvent was removed under reduced pressure, and the residue was redissolved in a minimum volume of CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e and applied to silica gel TLC plates. Elution with cyclohexane/dichloromethane (9:1, v/v) developed three bands which afforded, in order of elution, [(\u0026micro;-H)Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e6\u003c/sub\u003e(AsPh\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e(\u0026micro;-AsPh\u003csub\u003e2\u003c/sub\u003e)] (\u003cb\u003e4\u003c/b\u003e) (10 mg, 10%) as pale yellow crystals, [Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e5\u003c/sub\u003e(σ-Ph)(\u0026micro;-MeCO\u003csub\u003e2\u003c/sub\u003e)(\u0026micro;-AsPh\u003csub\u003e2\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e] (\u003cb\u003e5\u003c/b\u003e) (4.1 mg, 2%) as orange crystals and [HRe(CO)\u003csub\u003e4\u003c/sub\u003e(AsPh\u003csub\u003e3\u003c/sub\u003e)] (\u003cb\u003e6\u003c/b\u003e) (9.8 mg, 11%) as orange crystals after recrystallization from n-hexane/dichloromethane at \u003csup\u003e_\u003c/sup\u003e 4 \u003csup\u003eo\u003c/sup\u003eC. Compounds \u003cb\u003e4\u003c/b\u003e and \u003cb\u003e6\u003c/b\u003e are previously reported [\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e].\u003c/p\u003e\u003cp\u003eAnalytical and spectroscopic data for \u003cb\u003e5\u003c/b\u003e: Anal. Calcd. for C\u003csub\u003e37\u003c/sub\u003eH\u003csub\u003e28\u003c/sub\u003eO\u003csub\u003e7\u003c/sub\u003eRe\u003csub\u003e2\u003c/sub\u003eAs\u003csub\u003e2\u003c/sub\u003e: C, 40.15; H, 2.55. Found C, 40.05; H, 2.67%. IR (ν(CO), CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e): 2033 s, 2004 s, 1962 s, 1938 s, 1890 m cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. \u003csup\u003e1\u003c/sup\u003eH NMR (CDCl\u003csub\u003e3\u003c/sub\u003e): δ 7.95 (d, J\u0026thinsp;=\u0026thinsp;8 Hz, 2H), 7.79 (m, 2H), 7.63 (m, 3H), 7.56 (m, 3H), 7.44 (m, 7H), 7.40 (m, 3H), 7.18 (m, 3H), 7.12 m, 2H), 3.56 (s, 3H).\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec7\" class=\"Section2\"\u003e\u003ch2\u003e2.5 X-ray structure determination\u003c/h2\u003e\u003cp\u003eSingle crystals of complexes \u003cb\u003e1\u003c/b\u003e, \u003cb\u003e2\u003c/b\u003e, \u003cb\u003e3\u003c/b\u003e, and \u003cb\u003e5\u003c/b\u003e suitable for X-ray diffraction studies were obtained by slow diffusion of n-hexane into a CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e solution of each compound at 4 \u003csup\u003eo\u003c/sup\u003eC. Each suitable single crystal was mounted on a XtaLAB Synergy, Dualflex, HyPix, diffractometer using a Nylon loop and Paratone oil using Mo-Kα radiation (λ\u0026thinsp;=\u0026thinsp;0.71073). The diffraction data were collected at 149.99(10) K (for \u003cb\u003e1\u003c/b\u003e), 213 K (for \u003cb\u003e2\u003c/b\u003e), 213 K (for \u003cb\u003e3\u003c/b\u003e), and 206 K (for \u003cb\u003e5\u003c/b\u003e). Unit cell determination, data reduction, and absorption correction were done with SAINT V8.38A [\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e], and absorption corrections were applied using the program SADABS [\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e]. All the structures were solved by direct methods with the SHELXS [\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e] structure solution program and refined by full-matrix least-squares on F\u003csup\u003e2\u003c/sup\u003e using SHELXL [\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e] within the OLEX2 [\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e] graphical user interface. In all structures, non-hydrogen atoms were refined anisotropically, and the hydrogen atoms were included using a riding model. Relevant crystallographic parameters are given in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e.\u003c/p\u003e\u003cdiv id=\"Sec8\" class=\"Section2\"\u003e\u003ch2\u003e2.6 Computational methodology\u003c/h2\u003e\u003cp\u003eDensity Functional Theory (DFT) computations were employed to optimize the geometries of compounds \u003cb\u003e1\u003c/b\u003e, \u003cb\u003e2\u003c/b\u003e, \u003cb\u003e3\u003c/b\u003e, and \u003cb\u003e5\u003c/b\u003e in the gas phase. The coordinates of the experimental structures were used to optimize geometries. All calculations were carried out using the Gaussian16 [\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e] software package with the M06 functional [\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e]. The LANLeDZ [\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e] basis set was adopted to describe Mn, As, and Sb atoms, while the 6-311g(d,p) basis set was used for the remaining atoms. The absence of imaginary vibrational frequencies confirmed that all optimized structures correspond to the minima.\u003c/p\u003e\u003c/div\u003e"},{"header":"3. Results and discussion","content":"\u003cdiv id=\"Sec10\" class=\"Section2\"\u003e\u003ch2\u003e3.1. Reaction of [Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(NCMe)\u003csub\u003e2\u003c/sub\u003e] with AsPh\u003csub\u003e3\u003c/sub\u003e\u003c/h2\u003e\u003cp\u003eThe reaction of [Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(NCMe)\u003csub\u003e2\u003c/sub\u003e] with AsPh\u003csub\u003e3\u003c/sub\u003e in refluxing toluene afforded red crystals of [(\u0026micro;-H)(Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e7\u003c/sub\u003e(\u0026micro;-AsPh\u003csub\u003e2\u003c/sub\u003e)(AsPh\u003csub\u003e3\u003c/sub\u003e)] (\u003cb\u003e1\u003c/b\u003e) (20% yield) and pale yellow crystals of a previously reported compound [Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(\u0026micro;-AsPh\u003csub\u003e2\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e] (\u003cb\u003e2\u003c/b\u003e) (15% yield) (Scheme \u003cspan refid=\"Sch1\" class=\"InternalRef\"\u003e1\u003c/span\u003e) after chromatographic separation followed by recrystallization and manual separation of the crystals as mentioned in the experimental section.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eCompound \u003cb\u003e1\u003c/b\u003e is a precursor of \u003cb\u003e2\u003c/b\u003e. A toluene solution of \u003cb\u003e1\u003c/b\u003e was converted to \u003cb\u003e2\u003c/b\u003e when heated at 110 \u003csup\u003eo\u003c/sup\u003eC. Thus, compound \u003cb\u003e1\u003c/b\u003e formed first, and then it converted to \u003cb\u003e2\u003c/b\u003e. Both complexes were\u003c/p\u003e\u003cp\u003echaracterized by a combination of elemental analysis, \u0026sup1;H NMR, and IR spectroscopy, as well as single-crystal X-ray diffraction analyses.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eVery recently, we reported the Re\u0026ndash;As analogue of \u003cb\u003e1\u003c/b\u003e, [Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e7\u003c/sub\u003e(AsPh\u003csub\u003e3\u003c/sub\u003e)(\u0026micro;-AsPh\u003csub\u003e2\u003c/sub\u003e)(\u0026micro;-H)] [\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e], which is the first of its kind for Mn\u0026ndash;As complex. The solid-state structure of \u003cb\u003e1\u003c/b\u003e is shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e (left), with selected bond distances and angles in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e. The structure comprises a Mn\u003csub\u003e2\u003c/sub\u003e(\u0026micro;-As) triangular system with seven terminal carbonyl groups and an equatorially coordinated terminal AsPh\u003csub\u003e3\u003c/sub\u003e ligand. The two manganese atoms are mutually bound and simultaneously connected by a bridging hydride and an AsPh\u003csub\u003e2\u003c/sub\u003e ligand. The Mn\u0026thinsp;\u0026minus;\u0026thinsp;Mn bond distance at 2.9981(5) \u0026Aring; is significantly longer than that in the parent carbonyl [Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e10\u003c/sub\u003e] [2.90 \u0026Aring;] [\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e], which is most likely due to the bridging hydride and AsPh\u003csub\u003e2\u003c/sub\u003e ligands. The AsPh\u003csub\u003e2\u003c/sub\u003e ligand asymmetrically bridges the Mn\u0026ndash;Mn edge [Mn(1)\u0026ndash;As(1) 2.3365(4) and Mn(2)\u0026ndash;As(1) 2.3769(4) \u0026Aring;] with the shorter distance being associated with the Mn atom, Mn(1) that contains the bulky AsPh\u003csub\u003e3\u003c/sub\u003e ligand. The terminal Mn(1)\u0026ndash;As(2) bond distance of 2.4002(4) \u0026Aring; is significantly shorter than that observed in the analogous Re-As complex, [Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e7\u003c/sub\u003e(AsPh\u003csub\u003e3\u003c/sub\u003e)(\u0026micro;-AsPh\u003csub\u003e2\u003c/sub\u003e)(\u0026micro;-H)] [2.5125(6) \u0026Aring;] [\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e] as anticipated. The shortness of the proximate Mn(1)\u0026thinsp;\u0026minus;\u0026thinsp;As(1) bond is most likely due to a weaker trans-effect caused by the AsPh\u003csub\u003e3\u003c/sub\u003e ligand\u0026rsquo;s different π-back bonding properties compared to CO ligands that are trans to Mn\u0026thinsp;\u0026minus;\u0026thinsp;As bonds. Similar trans-effects involving the bridging AsPh\u003csub\u003e2\u003c/sub\u003e, SbPh\u003csub\u003e2,\u003c/sub\u003e and PPh\u003csub\u003e2\u003c/sub\u003e ligands were seen in the Re-As, Re\u0026thinsp;\u0026minus;\u0026thinsp;Sb, and Re\u0026thinsp;\u0026minus;\u0026thinsp;P bond distances in [Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e7\u003c/sub\u003e(AsPh\u003csub\u003e3\u003c/sub\u003e)(\u0026micro;-AsPh\u003csub\u003e2\u003c/sub\u003e)(\u0026micro;-H)] [\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e], [Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e7\u003c/sub\u003e(SbPh\u003csub\u003e3\u003c/sub\u003e)(\u0026micro;-SbPh\u003csub\u003e2\u003c/sub\u003e)(\u0026micro;-H)] [\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e], and [Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e7\u003c/sub\u003e(PPh\u003csub\u003e3\u003c/sub\u003e)(\u0026micro;-PPh\u003csub\u003e2\u003c/sub\u003e)(\u0026micro;-H)] [\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e]. The hydride ligand was crystallographically located and refined. As expected, the \u003csup\u003e1\u003c/sup\u003eH NMR spectroscopy shows a high-field singlet at δ \u0026ndash; 16.36 assigned to the bridging hydride ligand. Compound \u003cb\u003e1\u003c/b\u003e is a 34-valence electron compound with one metal\u0026thinsp;\u0026minus;\u0026thinsp;metal bond and structurally as well as electronically similar to that of [(\u0026micro;-H)Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e7\u003c/sub\u003e(AsPh\u003csub\u003e3\u003c/sub\u003e)(\u0026micro;-AsPh\u003csub\u003e2\u003c/sub\u003e)] [\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e], [Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e7\u003c/sub\u003e(SbPh\u003csub\u003e3\u003c/sub\u003e)(\u0026micro;-SbPh\u003csub\u003e2\u003c/sub\u003e)(\u0026micro;-H)] [\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e], and [Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e7\u003c/sub\u003e(PPh\u003csub\u003e3\u003c/sub\u003e)(\u0026micro;-PPh\u003csub\u003e2\u003c/sub\u003e)(\u0026micro;-H)] [\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e]. Scheme \u003cspan refid=\"Sch2\" class=\"InternalRef\"\u003e2\u003c/span\u003e illustrates a schematic representation of the probable mechanism of formation of \u003cb\u003e1\u003c/b\u003e. We believe that structures A to C or a combination of them are probable intermediates. The source of the hydride ligand in compound \u003cb\u003e1\u003c/b\u003e is most probably the solvent; similar events have also been seen previously [\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e, \u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e, \u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e]. All the Mn and As atoms are in the same plane, which made it easier to activate one Ph group from AsPh\u003csub\u003e3\u003c/sub\u003e to form the second \u0026micro;-AsPh\u003csub\u003e2,\u003c/sub\u003e resulting in the formation of \u003cb\u003e2\u003c/b\u003e.\u003c/p\u003e\u003cp\u003eAs described earlier, compound \u003cb\u003e2\u003c/b\u003e was previously crystallized from the reaction mixture by slow evaporation of toluene at room temperature [\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]. Diffraction data were collected at 273 K. We have recrystallized \u003cb\u003e2\u003c/b\u003e from a hexane/CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e solution at \u0026ndash; 4 \u003csup\u003eo\u003c/sup\u003eC and collected diffraction data at low temperature (150 K). The objective was to see if it crystallized in a different space group. An ORTEP diagram of the molecular structure of \u003cb\u003e2\u003c/b\u003e is represented in Fig.\u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e with selected bond distances in the caption. However, the structure is very similar to that previously reported by Miyamoto et al. [\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e].\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec11\" class=\"Section2\"\u003e\u003ch2\u003e2.2 Reaction of [Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(NCMe)\u003csub\u003e2\u003c/sub\u003e] with SbPh\u003csub\u003e3\u003c/sub\u003e\u003c/h2\u003e\u003cp\u003eIn contrast to the AsPh\u003csub\u003e3\u003c/sub\u003e chemistry discussed above, a similar reaction of [Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(NCMe)\u003csub\u003e2\u003c/sub\u003e] and SbPh\u003csub\u003e3\u003c/sub\u003e in toluene at 80 \u003csup\u003eo\u003c/sup\u003eC afforded [Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(\u0026micro;-SbPh\u003csub\u003e2\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e] (\u003cb\u003e3\u003c/b\u003e) as the sole product in 25% yield. We could not be successful in isolating any complex analogous to [Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e7\u003c/sub\u003e(AsPh\u003csub\u003e3\u003c/sub\u003e)(\u0026micro;-AsPh\u003csub\u003e2\u003c/sub\u003e)(\u0026micro;-H)] (\u003cb\u003e1\u003c/b\u003e). Spectroscopic data and a single-crystal X-ray study unambiguously characterized the new product \u003cb\u003e3\u003c/b\u003e. Compounds \u003cb\u003e2\u003c/b\u003e and \u003cb\u003e3\u003c/b\u003e are isostructural and isoelectronic. Figure\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e shows the molecular structure of \u003cb\u003e3\u003c/b\u003e, and selected bond lengths and angles are collected in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e. The dimer results from the two SbPh\u003csub\u003e2\u003c/sub\u003e ligands being in bridging coordination modes to two Mn(CO)\u003csub\u003e4\u003c/sub\u003e units. The Mn\u003csub\u003e2\u003c/sub\u003eAs\u003csub\u003e2\u003c/sub\u003e central core is a planar rhomb with the average bond length and angles, d(Mn\u0026mdash;Sb), \u0026ang;Sb\u0026ndash;Mn\u0026ndash;Sb, and \u0026ang;Mn\u0026ndash;Sb\u0026ndash;Mn, equal to 2.6228(12) \u0026Aring;, 78.07(4)\u0026deg;, and 101.94(4)\u0026deg;. While the Mn\u0026mdash;Sb bond lengths are significantly longer than expected. The Sb\u0026ndash;Mn\u0026ndash;Sb and Mn\u0026ndash;Sb\u0026ndash;Mn bond angles are comparable to those of its As-counterpart in \u003cb\u003e2\u003c/b\u003e [2.4752(5) \u0026Aring;, 78.993(13)\u0026deg; and 101.818(13)\u0026deg;], respectively. Analogous to \u003cb\u003e2\u003c/b\u003e, the four phenyl groups are located above and below this plane. There is no metal\u0026ndash;metal bond between the Re atoms. The Mn\u0026middot;\u0026middot;\u0026middot;Mn distance of 4.075 \u0026Aring; is clearly non-bonding as the Sb\u0026middot;\u0026middot;\u0026middot;Sb distance of 3.3035(17) \u0026Aring;. The molecule has a two-fold axis of symmetry that extends out perpendicularly to the Mn\u003csub\u003e2\u003c/sub\u003eSb\u003csub\u003e2\u003c/sub\u003e plane. In both Mn(CO)\u003csub\u003e4\u003c/sub\u003e units, the two sets of four Mn\u0026ndash;C distances are the same [1.827(5), 1.809(5), 1.849(5), 1.819(5) \u0026Aring;]. An interesting observation is that among the two sets of Mn(CO)\u003csub\u003e4\u003c/sub\u003e units, the trans Mn-C and C\u0026thinsp;=\u0026thinsp;O bond lengths are the same and are much closer due to the multiple bond nature of the carbonyls. The spectroscopic data for compound \u003cb\u003e3\u003c/b\u003e are consistent with the XRD data. For instance, the carbonyl region of the IR spectrum shows characteristic stretching vibrations for terminal CO, while the \u003csup\u003e1\u003c/sup\u003eH NMR spectrum exhibits characteristic aromatic signals for the \u0026micro;-SbPh\u003csub\u003e2\u003c/sub\u003e ligands.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec12\" class=\"Section2\"\u003e\u003ch2\u003e2.3. Reaction of [Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(NCMe)\u003csub\u003e2\u003c/sub\u003e] with AsPh\u003csub\u003e3\u003c/sub\u003e\u003c/h2\u003e\u003cp\u003eAs mentioned in the introduction, we have recently investigated the reactions of [Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e9\u003c/sub\u003e(NCMe)], and [Re\u003csub\u003e3\u003c/sub\u003e(CO)\u003csub\u003e11\u003c/sub\u003e(NCMe)(\u0026micro;-H)\u003csub\u003e3\u003c/sub\u003e] with AsPh₃ [\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e]. We have now investigated the reaction of [Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(NCMe)\u003csub\u003e2\u003c/sub\u003e] towards AsPh₃. The objectives were to see if the bis(acetonitrile) Re compound, which exists as a 2:1 equilibrium mixture of 2,6- and 2,3-isomers (Chart \u003cspan refid=\"Str2\" class=\"InternalRef\"\u003e2\u003c/span\u003e) [\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e], would provide structurally similar products to those obtained from [Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(NCMe)\u003csub\u003e2\u003c/sub\u003e] and/or [Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e9\u003c/sub\u003e(NCMe)].\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eThe reaction of [Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(NCMe)\u003csub\u003e2\u003c/sub\u003e] towards AsPh\u003csub\u003e3\u003c/sub\u003e in toluene at 80 \u003csup\u003eo\u003c/sup\u003eC followed by usual work up and chromatographic separation (detailed in experimental section) afforded the previously reported di\u0026ndash; and mononuclear compounds [Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e6\u003c/sub\u003e(AsPh\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e(\u0026micro;-AsPh\u003csub\u003e2\u003c/sub\u003e)(\u0026micro;-H)] (\u003cb\u003e4\u003c/b\u003e) [HRe(CO)\u003csub\u003e4\u003c/sub\u003e(AsPh\u003csub\u003e3\u003c/sub\u003e)] (\u003cb\u003e6\u003c/b\u003e) in 10 and 11% yields together with a new lower yield compound [Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e5\u003c/sub\u003e(σ-Ph)(\u0026micro;-MeCO\u003csub\u003e2\u003c/sub\u003e)(\u0026micro;-AsPh\u003csub\u003e2\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e] (\u003cb\u003e5\u003c/b\u003e) as orange crystals. (Scheme \u003cspan refid=\"Sch3\" class=\"InternalRef\"\u003e3\u003c/span\u003e) All attempts to increase the yield of \u003cb\u003e5\u003c/b\u003e were, however, unsuccessful.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eThe compound \u003cb\u003e5\u003c/b\u003e is characterized by a combination of elemental analysis, IR, and \u003csup\u003e1\u003c/sup\u003eH NMR spectroscopy, as well as single-crystal X-ray diffraction analysis. The molecular structure of \u003cb\u003e5\u003c/b\u003e is depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e, and the selected bond distances and angles are collected in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eThe molecular structure comprises two fused triangles of Re\u003csub\u003e2\u003c/sub\u003eAs. Unlike Mn\u003csub\u003e2\u003c/sub\u003eAs\u003csub\u003e2\u003c/sub\u003e or Mn\u003csub\u003e2\u003c/sub\u003eSb\u003csub\u003e2\u003c/sub\u003e, Re\u003csub\u003e2\u003c/sub\u003eAs\u003csub\u003e2\u003c/sub\u003e is neither fully planar nor diamond. The Re\u0026ndash;As distances are [Re(1)\u0026ndash;As(1) 2.5381(8), Re(1)\u0026ndash;As(2) 2.5607(8), Re(2)\u0026ndash;As(1) 2.4405(8), Re(2)\u0026ndash;As(2) 2.4483(9)] significantly shorter than that in [Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(\u0026micro;-AsPh\u003csub\u003e2\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e] [2.609(l) and 2.609(l) \u0026Aring;] [\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]. This result is due to (i) apart from the CO and AsPh\u003csub\u003e2\u003c/sub\u003e ligands, Re atoms are asymmetrically coordinated by a phenyl group (σ-Ph) and (ii) a bridging \u0026micro;-MeCO\u003csub\u003e2\u003c/sub\u003e. The \u0026micro;-MeCO\u003csub\u003e2\u003c/sub\u003e moiety is perpendicular to the Re\u003csub\u003e2\u003c/sub\u003eAs\u003csub\u003e2\u003c/sub\u003e trapezium and forms an unprecedented five-membered ring by cyclometallation of Re\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003eC. Although it is tough to predict how this ligand is formed, we can speculate that results from (i) one C\u0026ndash;C bond activation happened in toluene, (ii) the phenyl group added to one of the Re atoms, and (iii) the Me group attacks a carbon center of a CO\u003csub\u003e2\u003c/sub\u003e ligand to make \u0026micro;-MeCO\u003csub\u003e2\u003c/sub\u003e ligand. However, it is unclear whether the latter is formed as a result of the oxidation of a pre-bound carbonyl or via the absorption of CO\u003csub\u003e2\u003c/sub\u003e from the air during work-up. The binding of CO\u003csub\u003e2\u003c/sub\u003e to low-valent osmium clusters is surprisingly common [\u003cspan additionalcitationids=\"CR42\" citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e]. Earlier this year, we also observed a similar fusion to form a carboxylate (\u0026micro;-CO\u003csub\u003e2\u003c/sub\u003e) ligand in triosmium chemistry [\u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e]. However, the formation of a dirhenium carboxylate (Re\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e2\u003c/sub\u003e) system is unprecedented and interesting. The Re-O bond distances [Re(1)\u0026ndash;O(7) 2.171(4), Re(2)\u0026ndash;O(6) 2.167(4) \u0026Aring;] are similar to Os\u0026ndash;O bond lengths [2.136(7) and 2.099(7) \u0026Aring;] as expected. Given that there is one Re\u0026ndash;Re bond, then the complex is expected to have a valence electron count (VEC) of 34, which suggests that MeCO\u003csub\u003e2\u003c/sub\u003e acts as a 3-electron donor. The average terminal C\u0026ndash;O bond length is 1.14 (7) \u0026Aring;, while the C\u0026ndash;O bond lengths in the MeCO\u003csub\u003e2\u003c/sub\u003e ligand are C(6)\u0026ndash;O(6) 1.272(7) and C(6)\u0026ndash;O(7) 1.307(4) \u0026Aring;. Elongation of C(3)\u0026ndash;O(3) and C(5)\u0026ndash;O(5) bonds [1.155(7) and 1.157(7) \u0026Aring;] compared to other terminal C\u0026thinsp;=\u0026thinsp;O bonds [1.135 (7) \u0026Aring;] is the result of the trans effect \u0026micro;-MeCO\u003csub\u003e2\u003c/sub\u003e coordination. A similar reason is true for the Re(1)\u0026ndash;C(3) and Re(2)\u0026ndash;C(5) interactions, where the back bonding is stronger than that of the other Re\u0026ndash;C (from terminal CO) bonds.\u003c/p\u003e\u003cp\u003eThe spectroscopic data for compound \u003cb\u003e5\u003c/b\u003e are in accord with the solid-state structure. For instance, the carbonyl region of the IR spectrum shows characteristic stretching vibrations for terminal CO, while the \u003csup\u003e1\u003c/sup\u003eH NMR spectrum exhibits characteristic aromatic signals for the σ-Ph and \u0026micro;-AsPh\u003csub\u003e2\u003c/sub\u003e ligands.\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec13\" class=\"Section2\"\u003e\u003ch2\u003e2.4. DFT calculations\u003c/h2\u003e\u003cp\u003eThe geometries of compounds \u003cb\u003e1\u003c/b\u003e, \u003cb\u003e2\u003c/b\u003e, \u003cb\u003e3\u003c/b\u003e, and \u003cb\u003e5\u003c/b\u003e were optimized using density functional theory (DFT) calculations. The selected bond lengths and angles obtained from X-ray diffraction (XRD) data show good agreement with the DFT optimized values.\u003c/p\u003e\u003cp\u003eThe Wiberg bond index (WBI) values provide insight into the bonding characteristics of these compounds. For compound \u003cb\u003e1\u003c/b\u003e, the WBI values for Mn(1)\u0026ndash;Mn(2), As(2)\u0026ndash;Mn(1), and As(1)\u0026ndash;Mn(2) are 0.7858, 0.0.7282, 0.7077, respectively which are consistent with single bonds. In contrast, the WBI values for Mn(1)\u0026ndash;H(1), Mn(2)\u0026ndash;H(1) and Mn(1)\u0026ndash;Mn(2) are 0.3268, 0.3512 and 0.2365, respectively, indicating weak bonding interactions. For compound \u003cb\u003e2\u003c/b\u003e, the WBI values for As(1)\u0026ndash;Mn(1), As(1)\u0026ndash;Mn(2), As(2)\u0026ndash;Mn(1) and As(2)\u0026ndash;Mn(2) are 0.6853; 0.6863, 0.6863 and 0.6853, respectively. In \u003cb\u003e3\u003c/b\u003e, the WBI values for Sb(1)\u0026ndash;Mn(1), Sb(1)A\u0026ndash;Mn(1)A, Sb(1)A\u0026ndash;Mn(1), and Sb(1)-Mn(1)A have WBI values are 0.7019, 0.7113, 0.7019 and 0.7113, respectively. The WBI values in \u003cb\u003e2\u003c/b\u003e and \u003cb\u003e3\u003c/b\u003e fall in the range of 0.0.68\u0026thinsp;~\u0026thinsp;0.71, confirming that these are single covalent bonds. For \u003cb\u003e5\u003c/b\u003e, the WBI values for Re(1)\u0026ndash;As(1), Re(1)\u0026ndash;As(2), Re(2)\u0026ndash;As(1) and Re(2)\u0026ndash;As(2) are 0.6739, 0.6351, 0.8575, and 0.8551, respectively, all of which correspond to single covalent bonds. However, the WBI value for Re(1)\u0026ndash;Re(2) is 0.3195, suggesting a weak bonding interaction.\u003c/p\u003e"},{"header":"Summary and conclusions","content":"\u003cp\u003eIn summary, the bis(acetonitrile) compounds [M\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(NCMe)\u003csub\u003e2\u003c/sub\u003e] (Mn, Re) are found to react with AsPh\u003csub\u003e3\u003c/sub\u003e and SbPh\u003csub\u003e3\u003c/sub\u003e to yield a variety of activated products. It has been observed that the phenyl group is readily cleaved from AsPh\u003csub\u003e3\u003c/sub\u003e in its reactions with Mn(CO)\u003csub\u003e8\u003c/sub\u003e(NCMe)\u003csub\u003e2\u003c/sub\u003e] affording [Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e7\u003c/sub\u003e(\u0026micro;-AsPh\u003csub\u003e2\u003c/sub\u003e)(\u0026micro;-H)(AsPh\u003csub\u003e3\u003c/sub\u003e)] (\u003cb\u003e1\u003c/b\u003e) and [Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(\u0026micro;-AsPh\u003csub\u003e2\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e] (\u003cb\u003e2\u003c/b\u003e). Thermolysis of \u003cb\u003e1\u003c/b\u003e in refluxing toluene leads to the formation of \u003cb\u003e2\u003c/b\u003e. A probable reaction pathway leading to the formation of \u003cb\u003e2\u003c/b\u003e has been proposed. In contrast, [Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(\u0026micro;-AsPh\u003csub\u003e2\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e] (\u003cb\u003e2\u003c/b\u003e) was obtained as the only product when reacted with SbPh\u003csub\u003e3\u003c/sub\u003e. The manganese\u0026ndash;manganese bond was also cleaved in these reactions. Interestingly, there is no evidence in the formation of [Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(AsPh\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e] and [Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(SbPh\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e], which are the likely intermediates in the formation of \u003cb\u003e1\u003c/b\u003e\u0026ndash;\u003cb\u003e3\u003c/b\u003e. This is most likely As\u0026ndash;C and Sb\u0026ndash;C bond cleavage, which is facile at this temperature. In addition to the previously reported \u003cb\u003e4\u003c/b\u003e and \u003cb\u003e6\u003c/b\u003e, the σ-aryl compound [Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e5\u003c/sub\u003e(σ-Ph)(\u0026micro;-MeCO\u003csub\u003e2\u003c/sub\u003e)(\u0026micro;-AsPh\u003csub\u003e2\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e] (\u003cb\u003e5\u003c/b\u003e) was obtained in low yield, when [Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(NCMe)\u003csub\u003e2\u003c/sub\u003e] was reacted with AsPh\u003csub\u003e3\u003c/sub\u003e in toluene at 80 \u003csup\u003eo\u003c/sup\u003eC. At this end, we believe C\u0026ndash;CN bond activation, followed by a coupling of a CO\u003csub\u003e2\u003c/sub\u003e molecule from the atmosphere, produces MeCO\u003csub\u003e2,\u003c/sub\u003e which is a four-electron donor ligand.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eCRediT authorship contribution statement\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eMd. Jobayer Ahmed\u003c/strong\u003e:Investigation,Writing-original draft\u003cstrong\u003e, Md. Sohag Hasan\u003c/strong\u003e:Investigation,formal analysis\u003cstrong\u003e, Md. Atikul Islam:\u0026nbsp;\u003c/strong\u003eInvestigation,formal analysis\u003cstrong\u003e,\u003c/strong\u003e \u003cstrong\u003e\u0026nbsp; Md. Enamul Haque\u003c/strong\u003e:Computational analysis,\u003cstrong\u003e\u0026nbsp;Abdullah Al Mamun\u003c/strong\u003e: Investigation,formal analysis\u003cstrong\u003e, Joyanta K. Saha\u003c/strong\u003e: Computational analysis, Writing, \u003cstrong\u003eVladimir N. Nesterov\u003c/strong\u003e: X-ray data collection, Solving structures and editing, \u003cstrong\u003eShariff E. Kabir\u003c/strong\u003e: Supervision, Project administration, Writing, Review, and editing, \u003cstrong\u003eJagodish C. Sarker\u003c/strong\u003e: Supervision, Writing, Review and editing, Funding acquisition.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eDeclaration of competing interests\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare no competing interests.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFunding Declaration\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis research is funded by Jagannath University.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAcknowledgements\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eWe gratefully acknowledge the support of the Bangladesh University Grants Commission (UGC) and Jagannath University. SEK also acknowledges the UGC for the award of a Professorship. JCS thanks Mr Shah Md Ariful Abed and Professor A. J. Saleh Ahmed for their help in providing some chemicals used in this work.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eASSOCIATED CONTENT\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eSupplementary material associated with this article can be found in the online version. CCDC 2493935, 2493936, 2493937 and 2404750\u0026nbsp;contain supplementary crystallographic data for \u003cstrong\u003e1-3\u003c/strong\u003e and \u003cstrong\u003e5\u003c/strong\u003e, respectively. These data may be obtained free of charge from The Cambridge Crystallographic Data Center via www.ccdc.cam.ac.uk/data_request/cif, or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223\u0026ndash;336\u0026ndash;033; or e-mail: [email protected]. 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Host\u0026ndash;guest behavior of a heavy-atom heterocycle Re\u003csub\u003e4\u003c/sub\u003e(CO)\u003csub\u003e16\u003c/sub\u003e(\u0026micro;-SbPh\u003csub\u003e2\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e(\u0026micro;-H)\u003csub\u003e2\u003c/sub\u003e obtained from a palladium-assisted ring opening dimerization of Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(\u0026micro;-SbPh\u003csub\u003e2\u003c/sub\u003e)(\u0026micro;-H), \u003cem\u003eInorg. Chem.\u003c/em\u003e 54, 3536\u0026ndash;3544. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1021/acs.inorgchem.5b00080\u003c/span\u003e\u003cspan address=\"10.1021/acs.inorgchem.5b00080\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eE. Fujita, D. C. Grills, G. F. Manbeck, and D. E. Polyansky (2022). Understanding the role of inter- and intramolecular promoters in electro- and photochemical CO\u003csub\u003e2\u003c/sub\u003e reduction using Mn, Re, and Ru Catalysts. \u003cem\u003eAcc. Chem. Res.\u003c/em\u003e 55, 616\u0026ndash;628. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1021/acs.accounts.1c00616\u003c/span\u003e\u003cspan address=\"10.1021/acs.accounts.1c00616\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eR. D. Adams and W. C. Pearl Jr. (2010). Reactions of the platinum (tri-tert-butylphosphine) group with bridging SbPh\u003csub\u003e2\u003c/sub\u003e ligands in rhenium\u0026thinsp;\u0026ndash;\u0026thinsp;antimony carbonyl complexes. \u003cem\u003eInorg. Chem.\u003c/em\u003e 49, 6188\u0026ndash;6195. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1021/ic1008335\u003c/span\u003e\u003cspan address=\"10.1021/ic1008335\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eR. D. Adams and W. C. Pearl Jr. (2010). Reactions of bis(tri-tert-butylphosphine)platinum with metal hydride complexes. The reactions of Pt(P-t-Bu\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e with HRe(CO)\u003csub\u003e4\u003c/sub\u003eSbPh\u003csub\u003e3\u003c/sub\u003e. Organometallics 29, 3887\u0026ndash;3895, \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1021/om100569j\u003c/span\u003e\u003cspan address=\"10.1021/om100569j\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eSome selected reviews: (a) N.R. Champness and W. Levason (1994). Coordination chemistry of stibine and bismuthine ligands. \u003cem\u003eCoord. Chem. Rev\u003c/em\u003e. 33, 115\u0026ndash;217, \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/0010-8545(94)80058-8\u003c/span\u003e\u003cspan address=\"10.1016/0010-8545(94)80058-8\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e. (b) S. Schulz (2001). The chemistry of Group 13/15 compounds (III\u0026ndash;V compounds) with the higher homologues of Group 15, Sb and Bi. \u003cem\u003eCoord. Chem. Rev\u003c/em\u003e. 215, 1\u0026ndash;37, https://doi.org/10.1016/S0010-8545(00)00401-X; (c) S. L. Benjamin and G. Reid (2015). Neutral organoantimony(III) and organobismuth(III) ligands as acceptors in transition metal complexes\u0026ndash;Role of substituents and co-ligands. \u003cem\u003eCoord. Chem. Rev.\u003c/em\u003e 297\u0026ndash;298, 168\u0026ndash;180, https://doi.org/10.1016/j.ccr.2015.02.003; (d) W. Levason and G. Reid (2006). Developments in the coordination chemistry of stibine ligands. \u003cem\u003eCoord. Chem. Rev.\u003c/em\u003e 250, 2565\u0026ndash;2594, https://doi.org/10.1016/j.ccr.2006.03.024\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eSome selected papers: (a) D. A. Ortmann, O. Gevert, M. Laubender, and H. Werner (2001). Square-planar bis(triisopropylstibine)(olefin)iridium(I) complexes and their rearrangement to (η\u003csup\u003e3\u003c/sup\u003e-allyl)hydridoiridium(III) isomers. \u003cem\u003eOrganometallics\u003c/em\u003e 20, 1776\u0026ndash;1782, \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1021/om001078r\u003c/span\u003e\u003cspan address=\"10.1021/om001078r\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e; (b) S. Yasuike, S. Okajima, K. Yamaguchi, and J. Kurita (2003). 2,2\u0026prime;-Bis(diarylstibano)-1,1\u0026prime;-binaphthyls (BINASb); a useful chiral ligand for palladium-catalyzed asymmetric allylic alkylation, and the structure of a BINASb PdCl\u003csub\u003e2\u003c/sub\u003e complex. \u003cem\u003eTetrahedron Lett.\u003c/em\u003e 44, 6217\u0026ndash;6220, https://doi.org/10.1016/S0040-4039(03)01544-2; (c) S. Yasuike, S. Okajima, K. Yamaguchi, H. Seki, and J. Kurita (2003). New optically active organoantimony (BINASb) and bismuth (BINABi) compounds comprising a 1,1\u0026prime;-binaphthyl core: synthesis and their use in transition metal-catalyzed asymmetric hydrosilylation of ketones. \u003cem\u003eTetrahedron\u003c/em\u003e 59, 4959\u0026ndash;4966, https://doi.org/10.1016/S0040-4020(03)00740-3; (d) A.J. DiMaio, S.J. Geib, and A.L. Rheingold (1987). Synthesis and molecular structure of octacarbonyl- [bis(diphenylarsenido)]dirhenium, Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e[\u0026micro;-As(C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e5\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e]\u003csub\u003e2\u003c/sub\u003e, resulting from the Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e10\u003c/sub\u003e catalyzed disproportionation of phenylarsinidine, \u003cem\u003eJ. Organomet. Chem.\u003c/em\u003e 335, 97\u0026ndash;103, https://doi.org/10.1016/0022-328X(87)85177-X\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eR. F. Lambert (1961). Reaction of triphenylarsine with manganese carbonyl. Chemistry \u0026amp; Industry (London, United Kingdom) 830\u0026ndash;831.\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eN.J. Holmes, W. Levason, and M. Webster 1998). Triphenylstibine substituted manganese and rhenium carbonyls: synthesis and multinuclear NMR spectroscopic studies. X-ray crystal structures of ax-[Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e9\u003c/sub\u003e(SbPh\u003csub\u003e3\u003c/sub\u003e)], [Mn(CO)\u003csub\u003e5\u003c/sub\u003e(SbPh\u003csub\u003e3\u003c/sub\u003e)][CF\u003csub\u003e3\u003c/sub\u003eSO\u003csub\u003e3\u003c/sub\u003e] and fac-[Re(CO)\u003csub\u003e3\u003c/sub\u003eCl(SbPh\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e]. \u003cem\u003eJ. Organomet. Chem.\u003c/em\u003e 568, 213\u0026ndash;223, \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/S0022328X(98)00763-3\u003c/span\u003e\u003cspan address=\"10.1016/S0022328X(98)00763-3\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eR.D. Adams, B. Captain, W.C. Pearl Jr. (2008), Facile cleavage of a phenyl group from SbPh\u003csub\u003e3\u003c/sub\u003e by dirhenium carbonyl complexes. \u003cem\u003eJ. Organomet. Chem.\u003c/em\u003e 693, 1636\u0026ndash;1644. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.jorganchem.2007.11.028\u003c/span\u003e\u003cspan address=\"10.1016/j.jorganchem.2007.11.028\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eM. L. Bhowmik, M. A. A. Mamun, S. Ghosh, V. N. Nesterov, M. 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Thermolysis of rhenium carbonyl phosphine complexes Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e10\u0026ndash;n\u003c/sub\u003e(P(C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e5\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003en\u003c/sub\u003e (n\u0026thinsp;=\u0026thinsp;1, 2). \u003cem\u003eInorg. Chem.\u003c/em\u003e 27, 280\u0026ndash;286. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1021/ic00275a012\u003c/span\u003e\u003cspan address=\"10.1021/ic00275a012\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eJ. A. Iggo, M. J. Mays, P. R. Raithby, K. Hendrick (1983). Substitution and insertion reactions of the dinuclear manganese \u0026micro;-hydride complex [M\u003csub\u003e2\u003c/sub\u003e(\u0026micro;-H)(\u0026micro;-PPh\u003csub\u003e2\u003c/sub\u003e)(CO)\u003csub\u003e8\u003c/sub\u003e]; crystal structures of the complexes [Mn\u003csub\u003e2\u003c/sub\u003e(\u0026micro;-σ:η\u003csup\u003e2\u0026ndash;\u003c/sup\u003eCH\u0026thinsp;=\u0026thinsp;CH\u003csub\u003e2\u003c/sub\u003e)(\u0026micro;-PPh\u003csub\u003e2\u003c/sub\u003e)(CO)\u003csub\u003e7\u003c/sub\u003e] and [Mn\u003csub\u003e2\u003c/sub\u003e(\u0026micro;-H)(\u0026micro;-PPh\u003csub\u003e2\u003c/sub\u003e)(CO)\u003csub\u003e6\u003c/sub\u003e(CNBut)\u003csub\u003e2\u003c/sub\u003e]. \u003cem\u003eJ. Chem. Soc., Dalton Trans.\u003c/em\u003e 205\u0026ndash;215. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1039/DT9830000205\u003c/span\u003e\u003cspan address=\"10.1039/DT9830000205\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eG. R. John, B. F. G. Johnson, J. Lewis, and K. C. Wong (1979). The synthesis of clusters containing a \u0026micro;\u0026lt;background-color:#CCCCFF;usub\u0026gt;2\u0026lt;/background-color:#CCCCFF;usub\u0026gt;-CO\u0026lt;background-color:#CCCCFF;usub\u0026gt;2\u0026lt;/background-color:#CCCCFF;usub\u0026gt; linkage. \u003cem\u003eJ. Organomet. Chem.\u003c/em\u003e 169, C23\u0026ndash;26. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/S0022-328X(00)81164-X\u003c/span\u003e\u003cspan address=\"10.1016/S0022-328X(00)81164-X\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eB. F. G. Johnson, J. Lewis, P. R. Raithby, W. T. Wong (1991). Synthesis and X-ray structure of the osmium carbonyl anion [HOs\u003csub\u003e3\u003c/sub\u003e(CO)\u003csub\u003e10\u003c/sub\u003e\u0026middot;O\u003csub\u003e2\u003c/sub\u003eC\u0026middot;Os\u003csub\u003e6\u003c/sub\u003e(CO)\u003csub\u003e2\u003c/sub\u003eO]\u003csup\u003e\u0026ndash;\u003c/sup\u003e. \u003cem\u003eJ. Organomet. Chem.\u003c/em\u003e 401 C50\u0026ndash;C53. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/0022-328X(91)86240-Q\u003c/span\u003e\u003cspan address=\"10.1016/0022-328X(91)86240-Q\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eY. Chi, J. -W. Lan, S. -M. Peng, and G. -H. Lee (2001). Synthesis and characterization of tetra osmium carbonyl complexes containing a bridging CO\u003csub\u003e2\u003c/sub\u003e ligand. J. Clust. Sci. 12, 421\u0026ndash;432. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1023/A:1016625218456\u003c/span\u003e\u003cspan address=\"10.1023/A:1016625218456\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eN. C. Bhoumik, M. N. Huda, V. N. Nesterov, G. Hogarth, S. E. Kabir, and J. C. Sarker (2025). Reactivity of labile triosmium complexes, [Os\u003csub\u003e3\u003c/sub\u003e(CO)10(MeCN)\u003csub\u003e2\u003c/sub\u003e] and [Os\u003csub\u003e3\u003c/sub\u003e(CO)\u003csub\u003e10\u003c/sub\u003e(\u0026micro;-H)\u003csub\u003e2\u003c/sub\u003e] with tetraethylthiuram disulfide (disulfiram). \u003cem\u003eJ. Clust. Sci.\u003c/em\u003e 36, 34. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1007/s10876-024-02749-z\u003c/span\u003e\u003cspan address=\"10.1007/s10876-024-02749-z\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"},{"header":"Tables","content":"\u003cp\u003eTables 1 and 2 are available in the Supplementary Files section.\u003c/p\u003e"},{"header":"Charts and Schemes","content":"\u003cp\u003eCharts 1 and 2 are available in the Supplementary Files section\u003c/p\u003e\n\u003cp\u003eSchemes 1 to 3 are available in the Supplementary Files section\u003c/p\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"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":"journal-of-cluster-science","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"","sideBox":" Learn more about [Journal of Cluster Science](https://www.springer.com/journal/10876) ","snPcode":"10876","submissionUrl":"https://mc.manuscriptcentral.com/jocl","title":"Journal of Cluster Science","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Bimetallic complexes, As–C and Sb–C bond activations, Diphenyl arsenide, X-ray structure","lastPublishedDoi":"10.21203/rs.3.rs-7815224/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-7815224/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe reactivity of [M\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(NCMe)\u003csub\u003e2\u003c/sub\u003e] (Mn, Re) with EPh\u003csub\u003e3\u003c/sub\u003e (E\u0026thinsp;=\u0026thinsp;As, Sb) has been illustrated. Bimetallic manganese-arsenic complexes, [Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e7\u003c/sub\u003e(\u0026micro;-AsPh\u003csub\u003e2\u003c/sub\u003e)(AsPh\u003csub\u003e3\u003c/sub\u003e)(\u0026micro;-H)] (\u003cb\u003e1\u003c/b\u003e) and [Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(\u0026micro;-AsPh\u003csub\u003e2\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e] (\u003cb\u003e2\u003c/b\u003e) were produced from the reaction of [Mn₂(CO)\u003csub\u003e8\u003c/sub\u003e(NCMe)\u003csub\u003e2\u003c/sub\u003e] with AsPh\u003csub\u003e3\u003c/sub\u003e in refluxing toluene. The controlled experiment shows that \u003cb\u003e1\u003c/b\u003e is a precursor of \u003cb\u003e2\u003c/b\u003e. It can be speculated that activation of one phenyl group from the coordinated AsPh\u003csub\u003e3\u003c/sub\u003e of \u003cb\u003e1\u003c/b\u003e formed a second bridging (\u0026micro;-AsPh\u003csub\u003e2\u003c/sub\u003e) ligand. The cleaved phenyl group most probably combines with the departed edge-bridging hydride to produce benzene as a byproduct. In contrast, a similar reaction with SbPh\u003csub\u003e3\u003c/sub\u003e gave [Mn\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e8\u003c/sub\u003e(\u0026micro;-SbPh\u003csub\u003e2\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e] (\u003cb\u003e3\u003c/b\u003e) as the sole product. On the other hand, identical reaction of [Re₂(CO)\u003csub\u003e8\u003c/sub\u003e(NCMe)\u003csub\u003e2\u003c/sub\u003e] and AsPh\u003csub\u003e3\u003c/sub\u003e resulted a new type of rhenium-arsenic bimetallic complex [Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e5\u003c/sub\u003e(σ-Ph)(\u0026micro;-MeCO\u003csub\u003e2\u003c/sub\u003e)(\u0026micro;-AsPh\u003csub\u003e2\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e] (\u003cb\u003e5\u003c/b\u003e) along with two previously reported hydride compounds [Re\u003csub\u003e2\u003c/sub\u003e(CO)\u003csub\u003e6\u003c/sub\u003e(AsPh\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e(\u0026micro;-AsPh\u003csub\u003e2\u003c/sub\u003e)(\u0026micro;-H)] (\u003cb\u003e4\u003c/b\u003e) and [Re(CO)\u003csub\u003e4\u003c/sub\u003e(AsPh\u003csub\u003e3\u003c/sub\u003e)H] (\u003cb\u003e6\u003c/b\u003e). The coordination mechanism of the \u0026micro;-MeCO\u003csub\u003e2\u003c/sub\u003e ligand is unknown, as the source of MeCO\u003csub\u003e2\u003c/sub\u003e is unpredictable. However, we have observed similar incidents in Os\u003csub\u003e3\u003c/sub\u003e-dithiocarbamate chemistry. At this end, we believe C\u0026ndash;CN bond activation, followed by a coupling of a CO\u003csub\u003e2\u003c/sub\u003e molecule from the atm\u003cem\u003eosphe\u003c/em\u003ere, produces MeCO\u003csub\u003e2,\u003c/sub\u003e which is a four-electron donor ligand. Molecular structures of the new products \u003cb\u003e1\u003c/b\u003e, \u003cb\u003e3\u003c/b\u003e, and \u003cb\u003e5\u003c/b\u003e were unambiguously established through spectroscopic data and single-crystal X-ray diffraction studies. The bonding in these new complexes has been examined by density functional theory (DFT) calculations.\u003c/p\u003e","manuscriptTitle":"Carbon–arsine and carbon–antimony bonds activation of AsPh3 and SbPh3 at dimanganese and dirhenium centers in bimetallic clusters","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-11-04 16:50:59","doi":"10.21203/rs.3.rs-7815224/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2025-11-13T10:44:45+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-11-13T10:00:30+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-11-03T08:57:46+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-11-02T10:29:18+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"194681920000098042103610274372359981679","date":"2025-10-26T08:46:53+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"175867520011023621078769125451009521572","date":"2025-10-23T14:39:53+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"187002482389867744145850705288463499329","date":"2025-10-23T14:14:48+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-10-23T14:10:04+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-10-23T07:57:47+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-10-23T05:52:47+00:00","index":"","fulltext":""},{"type":"submitted","content":"Journal of Cluster Science","date":"2025-10-09T08:42:47+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"journal-of-cluster-science","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"","sideBox":" Learn more about [Journal of Cluster Science](https://www.springer.com/journal/10876) ","snPcode":"10876","submissionUrl":"https://mc.manuscriptcentral.com/jocl","title":"Journal of Cluster Science","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"65f71602-edb8-4772-9ecf-da0ef2ec070d","owner":[],"postedDate":"November 4th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"under-review","subjectAreas":[],"tags":[],"updatedAt":"2025-12-24T15:08:55+00:00","versionOfRecord":[],"versionCreatedAt":"2025-11-04 16:50:59","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-7815224","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-7815224","identity":"rs-7815224","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}