One-pot synthesis of unusual gold(I) cluster [Au 7 (Ph 3 P) 7 @C] 2+ in the presence of the macropolyhedral octadecahydro-eicosaborate anion [B 20 H 18 ] 2–

One-pot synthesis of unusual gold(I) cluster [Au 7 (Ph 3 P) 7 @C] 2+ in the presence of the macropolyhedral octadecahydro-eicosaborate anion [B 20 H 18 ] 2– | 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 One-pot synthesis of unusual gold(I) cluster [Au 7 (Ph 3 P) 7 @C] 2+ in the presence of the macropolyhedral octadecahydro-eicosaborate anion [B 20 H 18 ] 2– Varvara V. Avdeeva, Anna V. Vologzhanina, Valentin V. Novikov, and 3 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-3935964/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract The reaction between [Au(Ph3P)Cl] and [B20H18]2– in DMF gave unprecedented heptanuclear cationic cluster [Au7(Ph3P)7@C]2+ isolated as [Au7(Ph3P)7@C][B20H18][Au(Ph3P)Cl]·0.5DMF in one step. The final compound was studied by 11B NMR and IR spectroscopies, ESI MS, single-crystal and powder X-ray diffractions. No special reagents were used to obtain central carbon atom in the cluster [Au7(Ph3P)7@C]2+. gold complexation boron cluster anions gold clusters X-ray diffraction Figures Figure 1 INTRODUCTION The coordination chemistry of higher polyhedral borohydride dianions [B n H n ] 2– ( n = 6–12) [1–5] is rather interesting. Boron clusters being Pearson’s soft bases form numerous complexes with soft acids [6–9] , act as counterions with intermediate acids [10–14] , and reduce oxidation state of metals acting as hard acids thus oxidizing to borates [15] . In addition, boron clusters owing to their 3D aromaticity [16–18] participate in reactions of the substitution of terminal hydrogen atoms by various functional groups [19–21] . It was found that the closo -decaborate anion [B 10 H 10 ] 2– undergoes smooth oxidation in the presence of Fe(III) or Ce(IV) salts affording macropolyhedral boron cluster [ trans -B 20 H 18 ] 2– [22, 23] . This anion also can be used in coordination chemistry. A number of silver(I) and lead(II) compounds with the coordinated macropolyhedron were reported [24, 25] . Tris -chelate complexes [ML 3 ][B 20 H 18 ] (L = Mn, Cu, Fe, Co, Ni, Cd) [26–31] with the dimeric boron clusters as counterions are known. Gold complexation with boron clusters was studied in the presence of triphenylphosphine for the [B n H n ] 2– anions ( n = 6, 10, 12). The structures of [Au 2 (Ph 3 P) 4 [B 6 H 6 ]] [32] , [Au 3 (Ph 3 P) 3 [B 10 H 9 ]] [33] , and [Au 9 (PPh 3 ) 8 ][B 24 H 23 ] [33] were determined by X-ray diffraction (see SI, Figs. S1–S3). In addition, gold(I) compounds [Au(Ph 3 P) x ] 2 [B 12 Hal 12 ] (Hal = F, Cl, Br, I; x = 2, 3) with perhalogenated boron clusters as counterions were isolated [34] by the electrochemical reaction of (H 3 O) 2 [B 12 Hal 12 ] acids with Au 0 in the presence of Ph 3 P. Mononuclear complexes [(CH 3 CN) 2 Au][An] and [(Ph 3 P) 2 Au 2 Cl][An] [35] as well as binuclear complex [Ph 3 PAuClAuPh 3 P][B 12 Cl 11 (Me 3 N)] [36] with [An] = [B 12 Cl 11 (Me 3 N)] – were reported. In addition, polymeric chain gold(I) complex [Au(Ph 3 P) 2 ][Ag[B 12 H 12 ]] n is known [37] . First gold(III) complexes [AuLCl 2 ] 2 [B 20 H 18 ] (L = Bipy, Phen) were isolated recently. [38] . Au I PPh 3 species are known to form clusters consisting of 3–6 gold atoms with O [39] , S [40] , N [41] , P [42] , C [43, 44] , or B [45] atom in the center of the metal cluster. The central atom is generated with the specific reagents in each case. Gold also tends to form heterometallic compounds with copper and silver atoms coordinated outside the metal cage [46, 47] . Encouraged by the fact that gold clusters are formed by self-assembly in the presence of boron clusters as it was found for gold(I) reactions with [B 10 H 10 ] 2– and [B 12 H 12 ] 2– , herein we describe the results of [Au(Ph 3 P)Cl] complexation reactions in the presence of the [B 20 H 18 ] 2– anion, which gives an unusual [Au 7 (Ph 3 P) 7 @C] 2+ cationic gold cluster in one step. EXPERIMENTAL Methods Elemental analysis for carbon, hydrogen, and nitrogen was performed using a Carlo ErbaCHNS-3 FA 1108 automated elemental analyzer. Boron and metal content were determined on an iCAP 6300 Duo ICP emission spectrometer with inductively coupled plasma. Sample 1 ·0.5DMF was dried at 50°C to constant mass to form solvent-free sample 1 . IR spectra of compounds were recorded with Lumex Infralum FT-02 FTIR-spectrometer in the range of 4000–600 cm –1 at a resolution of 1 cm –1 . Samples were prepared as Nujol mulls; NaCl plates were used. Fresh crystals containing solvent molecules were used in measurements. 11 B NMR spectra of sample 1 ·0.5DMF in dmso- d 6 were recorded with a Bruker AC 200 spectrometer at a frequency of 64.297 MHz using BF 3 ·Et 2 O as an external standard. X-ray powder diffraction studies of crystal 1 ·0.5DMF were carried out on a Bruker D8 Advance X-ray diffractometer at the Shared Research Center of the Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences. The measurements were performed using Cu K α radiation in low-background cuvettes with a substrate of an oriented silicon single crystal in the 2θ angle range 5°–80° with a step of 0.01125°. To obtain diffraction patterns, sample 1 ·0.5DMF was carefully triturated in an agate mortar. X-ray powder diffraction pattern for 1 ·0.5DMF is shown in Fig. S4 and verify the purity of both compounds. Luminescence spectra. The emission spectrum of complex 1 ·0.5DMF in the solid state was obtained with a Fluorolog FL 3–22 spectrometer (Horiba-Jobin-Yvon, Edison, NJ, USA) which has a 450 W xenon lamp as the excitation source and an R-928 photomultiplier (Fig. S5). ESI mass spectrum of the reaction solution containing complex 1 ·0.5DMF was recorded on an API 3200 Qtrap spectrometer (Applied Biosystem, USA) and is shown in Fig. S6. Ionization conditions: turbo ion sputtering, ion sputtering, voltage ± 4500 V, declustering ± 12 V, flow rate 2–20 µL/min. The average analytical concentration of samples was 0.5–1.0 mg/L. X-ray diffraction studies of 1 ·0.5DMF were performed with a Bruker Apex DUO diffractometer (Cu K α radiation). The structure was solved by the SHELXT method [48] and refined by full-matrix least squares method against F 2 of all data using SHELXL-2014 [49] and OLEX2 [50] software. Non-hydrogen atoms were found on difference Fourier maps and refined with anisotropic displacement parameters. The positions of hydrogen atoms were calculated and included in refinement in isotropic approximation by the riding model with the U iso (H) = 1.5 U eq (C) for methyl groups and 1.2 U eq (C) for the other atoms, where U eq (C) are equivalent thermal parameters of parent atoms. Crystal data, details of data collection, and results of structure refinement are summarized in Table S1 . The crystallographic data were deposited with the Cambridge Crystallographic Data Center as supplementary publications under CCDC nos. 2126249. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures . Synthesis All reactions were carried out in air. DMF (HPLC grade), ethanol (95%), Ph 3 P (98%) were purchased from Sigma-Aldrich. (Et 3 NH) 2 [B 10 H 10 ] was synthesized from decaborane(14) [51] . (Et 3 NH) 2 [ trans -B 20 H 18 ] was prepared by oxidation of aqueous (Et 3 NH) 2 [B 10 H 10 ] with FeCl 3 [22, 52] . The obtained solid was dissolved in CH 3 CN/water mixture followed by the addition of aqueous Ph 4 PCl resulting in quantitative precipitation of (Ph 4 P) 2 [B 20 H 18 ]. [Au(Ph 3 P)Cl] was synthesized by chloroauric acid reduction with triphenylphosphine in 95% ethanol [53] . Synthesis of [Au 7 (Ph 3 P) 7 @C][B 20 H 18 ][Au(Ph 3 P)Cl] ∙ 0.5DMF ( 1 ∙0.5DMF) The reaction proceeds in air at room temperature. A solution of [Au(Ph 3 P)Cl] (5 mmol, 2.45 g) in DMF (5 ml) was added to a solution of (Ph 4 P) 2 [B 20 H 18 ] (0.5 mmol, 0.46 g) in DMF (10 ml) with stirring. The resulting colorless solution was allowed to stand in dark in air. After three days, the solution acquired the orange color. The formation of small light-orange crystals 1 ·0.5DMF was observed after a week of standing in air. The crystals were filtered off and dried in air. Yield, 30% based on boron (0.59 g). Anal. calcd. for Au 8 C 145 H 138 P 8 Cl B20 P 8 : Au, 37.49; C, 41.43; H, 3.31; B, 5.14. Found, %: Au, 38.28; C 42.13; H 3.11; B 5.09. IR (NaCl, ν, cm –1 ): ν(BH) 2541, 2522, 2503; δ(ВВН) 998; ν(CO) DMF 1674; 1584w, 1462, 1439, 1377, 1312w, 1179w, 1102, 748, 742, 723, 693. NMR 11 B (dmso- d 6 , ppm): 31.59 (d, 2B ap ), 17.46 (s, 2B, B2, B2’), − 5.49 (d, 2B eq ), − 11.15 (d, 4B eq ), − 14.48 (d, 4B eq ), − 18.07 (d, 4B), − 24.34 (d, 2B ap ). NMR 31 P (dmf- d 7 , ppm): 26.14 (s). Single crystal 1 ∙0.5DMF suitable for X-ray diffraction study was taken directly from the reaction solution. Crystal data, details of data collection, and results of structure refinement are summarized in Table S1 . The crystallographic data were deposited with the Cambridge Crystallographic Data Center as supplementary publications under CCDC nos. 2126249. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures . RESULTS AND DISCUSSION The reaction between [B 20 H 18 ] 2– and an excess of [Au(Ph 3 P)Cl] was performed in DMF. After a week, small light-orange crystals of complex [Au 7 (Ph 3 P) 7 @C][B 20 H 18 ][Au(Ph 3 P)Cl]∙0.5DMF ( 1 ∙0.5DMF) were isolated from the reaction solution according to the scheme. [B 20 H 18 ] 2– + 10 [Au(Ph 3 P)Cl][Au 7 (Ph 3 P) 7 @C][B 20 H 18 ][Au(Ph 3 P)Cl]∙0.5DMF ↓ In the IR spectrum of complex 1 ∙0.5DMF, a band with a maximum at 2522 cm –1 is observed, which related to the boron cluster anion acting as a counterion [27–30] . A number of bands attributed to coordinated Ph 3 P molecule are also observed. DMF molecules give a band near 1600 cm –1 originated from ν(CO), which is clearly observed in the spectrum. X-ray diffraction pattern of crystals 1 ·0.5DMF, luminescence spectrum of crystals 1 ·0.5DMF, ESI MS spectrum of the reaction solution are shown in Figs. S4–S6, respectively. Molecular view of compound 1 ·0.5DMF is shown in Fig. S7. According to X-ray diffraction study, an asymmetric unit of 1 ∙0.5DMF contains the eicosaborate dianion [B 20 H 18 ] 2– , a neutral [Au(Ph 3 P)Cl] complex, a [Au 7 (Ph 3 P) 7 @C] 2+ cation and one half solvent molecule (Fig. S7). Geometry of the linear [(Ph 3 P)AuCl] fragment is similar to that for AuCl·PPh 3 complex itself [54] and the boron cluster anion realizes the trans -configuration ( cis , iso , trans and fac isomers of the [B 20 H 18 ] 2– anion are discussed in review [55] ). The cation is presented by unprecedented carbon-centered gold [Au 7 @C] cluster (Fig. 1 ). Earlier a number of [Au 6 @C] octahedral clusters were synthesized [56–58] . Silver and copper atoms are able to cap faces of these octahedra or their trigonal-prismatic isomers to form highly luminescent complexes [46, 47, 59–61] . Clusters with hypercoordinated µ 7 - and µ 8 -carbon and boron atoms are also known, however, they are consist of up to 45 nickel atoms with additional copper, cobalt, or cadmium atoms [62] . Overall geometry of the metal core in 1 ∙0.5DMF (Fig. 1 ) can be described as a capped trigonal prism, where the capping atom is situated above a square prism face. The Au…Au distances and Au–P and Au–C bond lengths for this cluster as well as for previously reported [Au 6 (Ar 3 P) 6 @C] analogues are listed in Table 1 . Earlier described carbon-centered complexes include octahedral (OC) and trigonal-prismatic (TP) clusters. Both types can be capped with other group 11 metals (silver or copper). Geometry of the OC cluster remain nearly unchanged, for TP Ag 2 [Au 6 (Ar 3 P) 6 @C] [60, 61] and Cu 2 [Au 6 (Ar 3 P) 6 @C] [47] clusters the Au...Au distances are slightly shorter than those in OC ones. However, when the gold atom is added to OC cluster forming [Au 7 @C] it results in overall rearrangement of metal core into the capped trigonal prism with all Au...Au distances very close to each other and elongated Au–C bonds. The carbon atom is only 0.053(3) Å shifted from the center of mass of seven gold atoms. Table 1 Selected bond distances (Å) in carbon-centered gold clusters. CP a Au–Au P–Au Au–C References [Au 7 (Ph 3 P) 7 @C] СTP 2.7858(2)–2.9970(2) 2.2896(9)–2.3158(9) 2.226(3)–2.359(4) This work [Au 6 (Ar 3 P) 6 @C] OC 2.887–3.226 2.02–2.28 2.09–2.15 [46, 47, 56, 58, 59, 63, 64, 44] Ag 2 [Au 6 (Ar 3 P) 6 @C] COC 2.877–3.176 2.250–2.274 2.098–2.145 [46, 57, 60, 61] Ag 4 [Au 6 (Ar 3 P) 6 @C] COC 2.937–3.052 2.265–2.276 2.113–2.118 [59] Ag 6 [Au 6 (Ar 3 P) 6 @C] COC 2.914–2.959 2.293–2.303 2.14–2.16 [59] Ag 2 [Au 6 (Ar 3 P) 6 @C] CTP 2.741–2.903(2) 2.260–2.263 2.12–2.26 [60, 61] Cu 2 [Au 6 (Ar 3 P) 6 @C] CTP 2.718–2.867 2.252–2.256 2.157–2.168 [47] Cu 2 [Au 6 (Ar 3 P) 6 @C] COC 2.921–3.042 2.264–2.270 2.108–2.122 [47] a CP = coordination polyhedron: CTP is capped trigonal prism, OC is octahedron, COC is capped octahedron, CTP is capped trigonal prism. We assume that the central atom in the gold cluster is C. However, this fact cannot be stated unambiguously based on single-crystal X-ray diffraction data. We attempted to identify the central atom in the gold cluster by ESI mass-spectrometry. ESI MS spectra of complex 1 is given in SI (Fig. S6). ESI MS spectrum recorded in the negative mode (Fig. S6b) clearly shows the presence of the boron cluster anion (as [B 20 H 17 ] – particles), products of its degradation ([B 10 H 9 ] – ) and the associates of the boron cluster and cations (species Cat[An] – , where Cat = [AuPh 3 P] + or Ph 4 P + ; [An] 2– are B 10 or B 20 boron clusters. The [Au 7 @C] 2+ gold cluster highly likely degrades under ionization conditions giving smaller clusters [AuPh 3 P] + and [Au 2 (Ph 3 P) 2 ] + , which were detected as Cat[An] – ions. In the spectrum recorded in the positive mode (Fig. S6a) three main peaks are observed including the peaks of cations Ph 4 P + ( m / z = + 339.04), [Au(Ph 3 P)] 2+ ( m / z = + 228.93) and [Au 7 (Ph 3 P) 7 C][B 20 H 17 ] 2+ ( m / z = + 1730.18). Nevertheless, we should note that there is the possibility that an oxygen or nitrogen atom is present in the center of the gold cluster but the carbon atom seems to be the most probable as concluded based on X-ray diffraction data. Unfortunately, we failed in our attempts to get high-quality 13 C NMR spectrum to prove the carbon atom in the center of the cluster because of insufficient solubility of the target compound in solvents. In contrast to the previously reported carbon-centered gold clusters [46, 47, 59–61] , complex 1 does not exhibit prominent luminescence (Fig. S5). It seems that the reason is the presence of the boron clusters in the compound. Note that the decrease in luminescence intensity was also observed for Zn(II) and Cd(II) benzimidazole complexes with [B 10 H 10 ] 2– anions as compared to those with Cl – and NO 3 – anions [8] . It's also interesting to note that the charge balance in gold cluster [Au 7 L 7 @C] 2+ in compound 1 is different from those of other C-centered clusters. Typically, the [Au 6 L 6 @C] unit carries a (+ 2) charge resulting from six AuL + cations combined with a C 4– atom with 8 electrons. Thus, the [Au 7 (Ph 3 P) 7 C] 2+ unit seems to have an extra electron, which is highly likely a result of partial reduction by [B 20 H 18 ] 2– . Usually, special reagents are used to a desired central atom in the gold clusters. For example, tetrakis(dimethoxyboryl)methane C[B(OCH 3 ) 2 ] 4 was used to form [Au 6 (Ph 3 P) 6 C] 2+ from [Au(Ph 3 P)Cl] [44] . Herein we report un unprecedented one-pot synthesis to prepare seven-vertex gold cluster with a carbon atom in the center by self-assembly in the presence of the B 20 boron macropolyhedron. We believe that DMF is the source of the carbon atom formed as a result of DMF hydrolysis and further transformations of formic acid in the presence of boron clusters. DMF is known to degrade at various conditions giving carbon monoxide, methylamine, formaldehyde, formic acid [65–67] . During years of research of boron cluster complexation, we have noted DMF transformations in the presence of metal salts. Particularly, formation of [B 10 H 9 OCHNMe 2 ] 2– and [B 10 H 9 OH] 2– was observed in cobalt(II) and copper(II) complexation, respectively, with the [B 10 H 10 ] 2– anion in DMF [68, 69] ; DMF was the source of the substituent groups. In addition, the [Me 2 NH 2 ] + cation was isolated as borate [Me 2 NH 2 ][B 5 O 6 (OH) 4 ] in silver(I) complexation with [B 11 H 14 ] – in DMF [14] . The listed examples confirm the possibility of deep transformations of DMF in the presence of boron cluster anions. Moreover, when the studied reaction of [B 20 H 18 ] 2– with 10 eq. of [Au(Ph 3 P)Cl] was performed in CH 3 CN, C 2 H 5 OH, 1,2-dichloromethane or N,N-dimethylsulfoxide, no color change for the reaction mixture was noted and the only gold-containing product isolated from the reaction mixtures was the initial [Au(Ph 3 P)Cl] complex. When C 2 H 5 OH was used as the solvent, red-orange crystals precipitated, the parameters of which correspond to known gold cluster [Au 11 (PPh 3 ) 7 Cl 3 ] [71], which is known to form from [Au(Ph 3 P)Cl]. Thus, we can conclude that the presence of DMF molecules is crucial to get the final cationic complex [Au 7 (Ph 3 P) 7 @C] 2+ . In general, in reactions between [Au(Ph 3 P)Cl] and boron clusters [B 10 H 10 ] 2– [33] , [B 20 H 18 ] 2– (this study), and [B 24 H 23 ] 2– [33] there is a strong correlation between the size of the forming gold cluster and the size of the resulting boron cluster anion (see Figs. S1–S3). The formed gold clusters consist of three, seven, and nine atoms, respectively, no matter if the [Au(Ph 3 P)Cl] : [boron cluster anion] ratio is 5 or 10. If the ratio is set to 1 : 1, then cation-anionic complex can be isolated as it was found for the reaction of [Ag 2 [B 12 H 12 ]] with [Au(Ph 3 P)Cl], which gave ({Au(Ph 3 P) 2 }{Ag[B 12 H 12 ]}) n [37] . The formation of gold clusters in the presence of boron clusters can be explained by the tendency of gold(I) to form clusters in the presence of Ph 3 P and reducing agents; here, the boron cluster anions play the role of the reducing agents. In summary, the reaction of gold(I) complex [Au(PPh 3 )Cl] with the macropolyhedral boron anion [B 20 H 18 ] 2– was studied in DMF. A novel cationic gold cluster [Au 7 (Ph 3 P) 7 @C] 2+ was isolated in one step and characterized as crystals [Au 7 (Ph 3 P) 7 @C][B 20 H 18 ][Au(Ph 3 P)·0.5DMF. According to X-ray diffraction data, the gold cluster is found to be closely related to homo- and heterometallic [Au 6 (Ar 3 P)@C] 2+ clusters containing Group 11 metals and adopting µ 6 -C ligand. DMF molecules are assumed to be the source of the central carbon atom. Declarations ACKNOWLEDGMENTS This work was supported by the Ministry of Science and Higher Education of the Russian Federation as part of the State Assignment of the Kurnakov Institute of General and Inorganic Chemistry RAS and the A.N. Nesmeyanov Institute of Organoelement Compounds RAS in the field of fundamental research. Single-crystal X-ray diffraction study was carried out at the Centre for Molecular Composition Studies of the A.N. Nesmeyanov Institute of Organoelement Compounds RAS. Powder X-ray diffraction study was performed at the Shared Research Center of the Kurnakov Institute of General and Inorganic Chemistry RAS. The authors thank Belousova O.N. (the Kurnakov Institute) for measurements and interpretation of the IR spectra. Contributing roles VVA investigation, Writing - Original Draft; AVV Investigation, Writing - Review & Editing; VVN Investigation, Data curation; GAB Formal analysis, Visualization; ЕАM Conceptualization, Methodology; NTK Supervision. Ethical Approval Not applicable. Funding This work was supported by ongoing institutional funding. No additional grants to carry out or direct this particular research were obtained. Availability of data and materials Data available within the article or its supplementary materials Conflicts of interest. The authors declare that they have no conflicts of interest. Electronic Supplementary Information . The online version contains supplementary material available at DOI. Supplementary material includes experimental details and supporting data (Figs. S1–S7, Table S1). References Boron Science: New Technologies and Applications , Ed. N. S. Hosmane, CRC Press, 2012. I.B. 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Zhdanov, V.V. Avdeeva, V.I. Privalov, N.T. Kuznetsov, J. Clust. Sci . 2021, 32 , 755. V.V. Avdeeva, I. N. Polyakova, E. A. Malinina, L. V. Goeva, N. T. Kuznetsov, Inorg. Chim. Acta 2015, 428 , 154. B. S. Gutrath, U. Englert, Y. Wang, U. Simon, Eur. J. Inorg. Chem. 2013 , 2002 (2013). Additional Declarations No competing interests reported. Supplementary Files SI.doc Cite Share Download PDF Status: Posted Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. 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Avdeeva","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA9klEQVRIiWNgGAWjYHACAxSeHAMDY+MBkrQYA7U0kKYlsQFI4NXCPyN544OPbXYMBsfPPpP4uccufW374YYDjHsO49QicSOt2HBmWzKDwZl0M8meZ8m5284kAh32DLcWhjNnzKR5zjAzSDakMRvwHGDO3XYApOUAbi3yZ86Y//5zpp5Bsv8Zs+GfA/XpZucf4tdicLzHjJmh4jADv0Qa42OeA4cTzG4QsMXweFuxZE/FcR5+iWeMj2UOHDfcdgNoS8KBdJxa5A4zb/zww6Bajo0/jeHgmwPV8mbn0x8++HDAGrf3oYAHlZtAUMMoGAWjYBSMAnwAAFWwXB+o6EO5AAAAAElFTkSuQmCC","orcid":"","institution":"Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences","correspondingAuthor":true,"prefix":"","firstName":"Varvara","middleName":"V.","lastName":"Avdeeva","suffix":""},{"id":272951385,"identity":"cb391311-e3ea-4f38-b3b2-ba360540e0fe","order_by":1,"name":"Anna V. Vologzhanina","email":"","orcid":"","institution":"A. N. Nesmeyanov Institute of Organoelement Compounds","correspondingAuthor":false,"prefix":"","firstName":"Anna","middleName":"V.","lastName":"Vologzhanina","suffix":""},{"id":272951386,"identity":"f5eb3b06-7c09-4182-bf10-02e0643d5b68","order_by":2,"name":"Valentin V. Novikov","email":"","orcid":"","institution":"Universitat de Barcelona","correspondingAuthor":false,"prefix":"","firstName":"Valentin","middleName":"V.","lastName":"Novikov","suffix":""},{"id":272951387,"identity":"b4a3ad04-4e0a-4c63-999b-7580c90b60d0","order_by":3,"name":"Grigorii A. Buzanov","email":"","orcid":"","institution":"Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences","correspondingAuthor":false,"prefix":"","firstName":"Grigorii","middleName":"A.","lastName":"Buzanov","suffix":""},{"id":272951388,"identity":"3f589b30-e44d-4c3d-80c4-5ba7eb71f43d","order_by":4,"name":"Еlena А. Malinina","email":"","orcid":"","institution":"Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences","correspondingAuthor":false,"prefix":"","firstName":"Еlena","middleName":"А.","lastName":"Malinina","suffix":""},{"id":272951389,"identity":"c29ec202-198d-44c8-9540-6451cb366cc8","order_by":5,"name":"Nikolay T. Kuznetsov","email":"","orcid":"","institution":"Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences","correspondingAuthor":false,"prefix":"","firstName":"Nikolay","middleName":"T.","lastName":"Kuznetsov","suffix":""}],"badges":[],"createdAt":"2024-02-07 06:15:36","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-3935964/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-3935964/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":51236245,"identity":"25f92457-2bab-4ef7-a67c-7a02fcfbbfe2","added_by":"auto","created_at":"2024-02-16 16:39:53","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":55635,"visible":true,"origin":"","legend":"\u003cp\u003eMolecular view of the [Au\u003csub\u003e7\u003c/sub\u003e(Ph\u003csub\u003e3\u003c/sub\u003eP)\u003csub\u003e7\u003c/sub\u003e@C]\u003csup\u003e2+\u003c/sup\u003e cation.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-3935964/v1/796cc6259ecf6b00cf5156c9.png"},{"id":52292128,"identity":"5d5640b8-125f-432c-8e95-4a4ad285ef52","added_by":"auto","created_at":"2024-03-08 16:58:02","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":377984,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-3935964/v1/676f0cd3-ea0a-4c96-8af7-3d6f406d591e.pdf"},{"id":51236246,"identity":"ae96398d-f35d-4a23-b82e-4bf80ce44d52","added_by":"auto","created_at":"2024-02-16 16:39:53","extension":"doc","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":976384,"visible":true,"origin":"","legend":"","description":"","filename":"SI.doc","url":"https://assets-eu.researchsquare.com/files/rs-3935964/v1/d5fc431bed577116ba44787c.doc"}],"financialInterests":"No competing interests reported.","formattedTitle":"One-pot synthesis of unusual gold(I) cluster [Au 7 (Ph 3 P) 7 @C] 2+ in the presence of the macropolyhedral octadecahydro-eicosaborate anion [B 20 H 18 ] 2–","fulltext":[{"header":"INTRODUCTION","content":"\u003cp\u003eThe coordination chemistry of higher polyhedral borohydride dianions [B\u003csub\u003e\u003cem\u003en\u003c/em\u003e\u003c/sub\u003eH\u003csub\u003e\u003cem\u003en\u003c/em\u003e\u003c/sub\u003e]\u003csup\u003e2\u0026ndash;\u003c/sup\u003e (\u003cem\u003en\u003c/em\u003e\u0026thinsp;=\u0026thinsp;6\u0026ndash;12) \u003csup\u003e[1\u0026ndash;5]\u003c/sup\u003e is rather interesting. Boron clusters being Pearson\u0026rsquo;s soft bases form numerous complexes with soft acids\u003csup\u003e[6\u0026ndash;9]\u003c/sup\u003e, act as counterions with intermediate acids \u003csup\u003e[10\u0026ndash;14]\u003c/sup\u003e, and reduce oxidation state of metals acting as hard acids thus oxidizing to borates \u003csup\u003e[15]\u003c/sup\u003e. In addition, boron clusters owing to their 3D aromaticity \u003csup\u003e[16\u0026ndash;18]\u003c/sup\u003e participate in reactions of the substitution of terminal hydrogen atoms by various functional groups \u003csup\u003e[19\u0026ndash;21]\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eIt was found that the \u003cem\u003ecloso\u003c/em\u003e-decaborate anion [B\u003csub\u003e10\u003c/sub\u003eH\u003csub\u003e10\u003c/sub\u003e]\u003csup\u003e2\u0026ndash;\u003c/sup\u003e undergoes smooth oxidation in the presence of Fe(III) or Ce(IV) salts affording macropolyhedral boron cluster [\u003cem\u003etrans\u003c/em\u003e-B\u003csub\u003e20\u003c/sub\u003eH\u003csub\u003e18\u003c/sub\u003e]\u003csup\u003e2\u0026ndash; [22, 23]\u003c/sup\u003e. This anion also can be used in coordination chemistry. A number of silver(I) and lead(II) compounds with the coordinated macropolyhedron were reported \u003csup\u003e[24, 25]\u003c/sup\u003e. \u003cem\u003eTris\u003c/em\u003e-chelate complexes [ML\u003csub\u003e3\u003c/sub\u003e][B\u003csub\u003e20\u003c/sub\u003eH\u003csub\u003e18\u003c/sub\u003e] (L\u0026thinsp;=\u0026thinsp;Mn, Cu, Fe, Co, Ni, Cd) \u003csup\u003e[26\u0026ndash;31]\u003c/sup\u003e with the dimeric boron clusters as counterions are known.\u003c/p\u003e \u003cp\u003eGold complexation with boron clusters was studied in the presence of triphenylphosphine for the [B\u003csub\u003e\u003cem\u003en\u003c/em\u003e\u003c/sub\u003eH\u003csub\u003e\u003cem\u003en\u003c/em\u003e\u003c/sub\u003e]\u003csup\u003e2\u0026ndash;\u003c/sup\u003e anions (\u003cem\u003en\u003c/em\u003e\u0026thinsp;=\u0026thinsp;6, 10, 12). The structures of [Au\u003csub\u003e2\u003c/sub\u003e(Ph\u003csub\u003e3\u003c/sub\u003eP)\u003csub\u003e4\u003c/sub\u003e[B\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e]] \u003csup\u003e[32]\u003c/sup\u003e, [Au\u003csub\u003e3\u003c/sub\u003e(Ph\u003csub\u003e3\u003c/sub\u003eP)\u003csub\u003e3\u003c/sub\u003e[B\u003csub\u003e10\u003c/sub\u003eH\u003csub\u003e9\u003c/sub\u003e]] \u003csup\u003e[33]\u003c/sup\u003e, and [Au\u003csub\u003e9\u003c/sub\u003e(PPh\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e8\u003c/sub\u003e][B\u003csub\u003e24\u003c/sub\u003eH\u003csub\u003e23\u003c/sub\u003e] \u003csup\u003e[33]\u003c/sup\u003e were determined by X-ray diffraction (see SI, Figs. S1\u0026ndash;S3). In addition, gold(I) compounds [Au(Ph\u003csub\u003e3\u003c/sub\u003eP)\u003csub\u003e\u003cem\u003ex\u003c/em\u003e\u003c/sub\u003e]\u003csub\u003e2\u003c/sub\u003e[B\u003csub\u003e12\u003c/sub\u003eHal\u003csub\u003e12\u003c/sub\u003e] (Hal\u0026thinsp;=\u0026thinsp;F, Cl, Br, I; \u003cem\u003ex\u003c/em\u003e\u0026thinsp;=\u0026thinsp;2, 3) with perhalogenated boron clusters as counterions were isolated \u003csup\u003e[34]\u003c/sup\u003e by the electrochemical reaction of (H\u003csub\u003e3\u003c/sub\u003eO)\u003csub\u003e2\u003c/sub\u003e[B\u003csub\u003e12\u003c/sub\u003eHal\u003csub\u003e12\u003c/sub\u003e] acids with Au\u003csup\u003e0\u003c/sup\u003e in the presence of Ph\u003csub\u003e3\u003c/sub\u003eP. Mononuclear complexes [(CH\u003csub\u003e3\u003c/sub\u003eCN)\u003csub\u003e2\u003c/sub\u003eAu][An] and [(Ph\u003csub\u003e3\u003c/sub\u003eP)\u003csub\u003e2\u003c/sub\u003eAu\u003csub\u003e2\u003c/sub\u003eCl][An] \u003csup\u003e[35]\u003c/sup\u003e as well as binuclear complex [Ph\u003csub\u003e3\u003c/sub\u003ePAuClAuPh\u003csub\u003e3\u003c/sub\u003eP][B\u003csub\u003e12\u003c/sub\u003eCl\u003csub\u003e11\u003c/sub\u003e(Me\u003csub\u003e3\u003c/sub\u003eN)] \u003csup\u003e[36]\u003c/sup\u003e with [An] = [B\u003csub\u003e12\u003c/sub\u003eCl\u003csub\u003e11\u003c/sub\u003e(Me\u003csub\u003e3\u003c/sub\u003eN)]\u003csup\u003e\u0026ndash;\u003c/sup\u003e were reported. In addition, polymeric chain gold(I) complex [Au(Ph\u003csub\u003e3\u003c/sub\u003eP)\u003csub\u003e2\u003c/sub\u003e][Ag[B\u003csub\u003e12\u003c/sub\u003eH\u003csub\u003e12\u003c/sub\u003e]]\u003csub\u003e\u003cem\u003en\u003c/em\u003e\u003c/sub\u003e is known \u003csup\u003e[37]\u003c/sup\u003e. First gold(III) complexes [AuLCl\u003csub\u003e2\u003c/sub\u003e]\u003csub\u003e2\u003c/sub\u003e[B\u003csub\u003e20\u003c/sub\u003eH\u003csub\u003e18\u003c/sub\u003e] (L\u0026thinsp;=\u0026thinsp;Bipy, Phen) were isolated recently.\u003csup\u003e[38]\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eAu\u003csup\u003eI\u003c/sup\u003ePPh\u003csub\u003e3\u003c/sub\u003e species are known to form clusters consisting of 3\u0026ndash;6 gold atoms with O \u003csup\u003e[39]\u003c/sup\u003e, S \u003csup\u003e[40]\u003c/sup\u003e, N \u003csup\u003e[41]\u003c/sup\u003e, P \u003csup\u003e[42]\u003c/sup\u003e, C \u003csup\u003e[43, 44]\u003c/sup\u003e, or B \u003csup\u003e[45]\u003c/sup\u003e atom in the center of the metal cluster. The central atom is generated with the specific reagents in each case. Gold also tends to form heterometallic compounds with copper and silver atoms coordinated outside the metal cage \u003csup\u003e[46, 47]\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eEncouraged by the fact that gold clusters are formed by self-assembly in the presence of boron clusters as it was found for gold(I) reactions with [B\u003csub\u003e10\u003c/sub\u003eH\u003csub\u003e10\u003c/sub\u003e]\u003csup\u003e2\u0026ndash;\u003c/sup\u003e and [B\u003csub\u003e12\u003c/sub\u003eH\u003csub\u003e12\u003c/sub\u003e]\u003csup\u003e2\u0026ndash;\u003c/sup\u003e, herein we describe the results of [Au(Ph\u003csub\u003e3\u003c/sub\u003eP)Cl] complexation reactions in the presence of the [B\u003csub\u003e20\u003c/sub\u003eH\u003csub\u003e18\u003c/sub\u003e]\u003csup\u003e2\u0026ndash;\u003c/sup\u003e anion, which gives an unusual [Au\u003csub\u003e7\u003c/sub\u003e(Ph\u003csub\u003e3\u003c/sub\u003eP)\u003csub\u003e7\u003c/sub\u003e@C]\u003csup\u003e2+\u003c/sup\u003e cationic gold cluster in one step.\u003c/p\u003e"},{"header":"EXPERIMENTAL","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e\n \u003ch2\u003eMethods\u003c/h2\u003e\n \u003cp\u003e\u003cstrong\u003eElemental analysis\u003c/strong\u003e for carbon, hydrogen, and nitrogen was performed using a Carlo ErbaCHNS-3 FA 1108 automated elemental analyzer. Boron and metal content were determined on an iCAP 6300 Duo ICP emission spectrometer with inductively coupled plasma. Sample \u003cstrong\u003e1\u003c/strong\u003e\u0026middot;0.5DMF was dried at 50\u0026deg;C to constant mass to form solvent-free sample \u003cstrong\u003e1\u003c/strong\u003e.\u003c/p\u003e\n \u003cp\u003e\u003cstrong\u003eIR spectra\u003c/strong\u003e of compounds were recorded with Lumex Infralum FT-02 FTIR-spectrometer in the range of 4000\u0026ndash;600 cm\u003csup\u003e\u0026ndash;1\u003c/sup\u003e at a resolution of 1 cm\u003csup\u003e\u0026ndash;1\u003c/sup\u003e. Samples were prepared as Nujol mulls; NaCl plates were used. Fresh crystals containing solvent molecules were used in measurements.\u003c/p\u003e\n \u003cp\u003e\u003csup\u003e\u0026nbsp;\u003cstrong\u003e11\u003c/strong\u003e\u0026nbsp;\u003c/sup\u003e \u003cstrong\u003eB NMR spectra\u003c/strong\u003e of sample \u003cstrong\u003e1\u003c/strong\u003e\u0026middot;0.5DMF in dmso-\u003cem\u003ed\u003c/em\u003e\u003csub\u003e6\u003c/sub\u003e were recorded with a Bruker AC 200 spectrometer at a frequency of \u003cem\u003e64.297\u003c/em\u003e MHz using BF\u003csub\u003e3\u003c/sub\u003e\u0026middot;Et\u003csub\u003e2\u003c/sub\u003eO as an external standard.\u003c/p\u003e\n \u003cp\u003e\u003cstrong\u003eX-ray powder diffraction\u003c/strong\u003e studies of crystal \u003cstrong\u003e1\u003c/strong\u003e\u0026middot;0.5DMF were carried out on a Bruker D8 Advance X-ray diffractometer at the Shared Research Center of the Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences. The measurements were performed using Cu\u003cem\u003eK\u003c/em\u003e\u003csub\u003e\u0026alpha;\u003c/sub\u003e radiation in low-background cuvettes with a substrate of an oriented silicon single crystal in the 2\u0026theta; angle range 5\u0026deg;\u0026ndash;80\u0026deg; with a step of 0.01125\u0026deg;. To obtain diffraction patterns, sample \u003cstrong\u003e1\u003c/strong\u003e\u0026middot;0.5DMF was carefully triturated in an agate mortar. X-ray powder diffraction pattern for \u003cstrong\u003e1\u003c/strong\u003e\u0026middot;0.5DMF is shown in Fig. S4 and verify the purity of both compounds.\u003c/p\u003e\n \u003cp\u003e\u003cstrong\u003eLuminescence spectra.\u003c/strong\u003e The emission spectrum of complex \u003cstrong\u003e1\u003c/strong\u003e\u0026middot;0.5DMF in the solid state was obtained with a Fluorolog FL 3\u0026ndash;22 spectrometer (Horiba-Jobin-Yvon, Edison, NJ, USA) which has a 450 W xenon lamp as the excitation source and an R-928 photomultiplier (Fig. S5).\u003c/p\u003e\n \u003cp\u003e\u003cstrong\u003eESI mass spectrum\u003c/strong\u003e of the reaction solution containing complex \u003cstrong\u003e1\u003c/strong\u003e\u0026middot;0.5DMF was recorded on an API 3200 Qtrap spectrometer (Applied Biosystem, USA) and is shown in Fig. S6. Ionization conditions: turbo ion sputtering, ion sputtering, voltage\u0026thinsp;\u0026plusmn;\u0026thinsp;4500 V, declustering\u0026thinsp;\u0026plusmn;\u0026thinsp;12 V, flow rate 2\u0026ndash;20 \u0026micro;L/min. The average analytical concentration of samples was 0.5\u0026ndash;1.0 mg/L.\u003c/p\u003e\n \u003cp\u003e\u003cstrong\u003eX-ray diffraction studies\u003c/strong\u003e of \u003cstrong\u003e1\u003c/strong\u003e\u0026middot;0.5DMF were performed with a Bruker Apex DUO diffractometer (Cu\u003cem\u003eK\u003c/em\u003e\u003csub\u003e\u0026alpha;\u003c/sub\u003e radiation). The structure was solved by the SHELXT method \u003csup\u003e[48]\u003c/sup\u003e and refined by full-matrix least squares method against \u003cem\u003eF\u003c/em\u003e\u003csup\u003e2\u003c/sup\u003e of all data using SHELXL-2014 \u003csup\u003e[49]\u003c/sup\u003e and OLEX2 \u003csup\u003e[50]\u003c/sup\u003e software. Non-hydrogen atoms were found on difference Fourier maps and refined with anisotropic displacement parameters. The positions of hydrogen atoms were calculated and included in refinement in isotropic approximation by the riding model with the \u003cem\u003eU\u003c/em\u003e\u003csub\u003eiso\u003c/sub\u003e(H)\u0026thinsp;=\u0026thinsp;1.5\u003cem\u003eU\u003c/em\u003e\u003csub\u003eeq\u003c/sub\u003e(C) for methyl groups and 1.2\u003cem\u003eU\u003c/em\u003e\u003csub\u003eeq\u003c/sub\u003e(C) for the other atoms, where \u003cem\u003eU\u003c/em\u003e\u003csub\u003eeq\u003c/sub\u003e(C) are equivalent thermal parameters of parent atoms.\u003c/p\u003e\n \u003cp\u003eCrystal data, details of data collection, and results of structure refinement are summarized in Table \u003cspan class=\"InternalRef\"\u003eS1\u003c/span\u003e. The crystallographic data were deposited with the Cambridge Crystallographic Data Center as supplementary publications under CCDC nos. 2126249. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre \u003cem\u003evia\u003c/em\u003e \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ewww.ccdc.cam.ac.uk/structures\u003c/span\u003e\u003c/span\u003e.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec4\" class=\"Section2\"\u003e\n \u003ch2\u003eSynthesis\u003c/h2\u003e\n \u003cp\u003eAll reactions were carried out in air. DMF (HPLC grade), ethanol (95%), Ph\u003csub\u003e3\u003c/sub\u003eP (98%) were purchased from Sigma-Aldrich. (Et\u003csub\u003e3\u003c/sub\u003eNH)\u003csub\u003e2\u003c/sub\u003e[B\u003csub\u003e10\u003c/sub\u003eH\u003csub\u003e10\u003c/sub\u003e] was synthesized from decaborane(14) \u003csup\u003e[51]\u003c/sup\u003e. (Et\u003csub\u003e3\u003c/sub\u003eNH)\u003csub\u003e2\u003c/sub\u003e[\u003cem\u003etrans\u003c/em\u003e-B\u003csub\u003e20\u003c/sub\u003eH\u003csub\u003e18\u003c/sub\u003e] was prepared by oxidation of aqueous (Et\u003csub\u003e3\u003c/sub\u003eNH)\u003csub\u003e2\u003c/sub\u003e[B\u003csub\u003e10\u003c/sub\u003eH\u003csub\u003e10\u003c/sub\u003e] with FeCl\u003csub\u003e3\u003c/sub\u003e \u003csup\u003e[22, 52]\u003c/sup\u003e. The obtained solid was dissolved in CH\u003csub\u003e3\u003c/sub\u003eCN/water mixture followed by the addition of aqueous Ph\u003csub\u003e4\u003c/sub\u003ePCl resulting in quantitative precipitation of (Ph\u003csub\u003e4\u003c/sub\u003eP)\u003csub\u003e2\u003c/sub\u003e[B\u003csub\u003e20\u003c/sub\u003eH\u003csub\u003e18\u003c/sub\u003e]. [Au(Ph\u003csub\u003e3\u003c/sub\u003eP)Cl] was synthesized by chloroauric acid reduction with triphenylphosphine in 95% ethanol \u003csup\u003e[53]\u003c/sup\u003e.\u003c/p\u003e\n \u003cp\u003e\u003cem\u003eSynthesis of [Au\u003c/em\u003e \u003csub\u003e\u0026nbsp;\u003cem\u003e7\u003c/em\u003e\u0026nbsp;\u003c/sub\u003e \u003cem\u003e(Ph\u003c/em\u003e \u003csub\u003e\u0026nbsp;\u003cem\u003e3\u003c/em\u003e\u0026nbsp;\u003c/sub\u003e \u003cem\u003eP)\u003c/em\u003e \u003csub\u003e\u0026nbsp;\u003cem\u003e7\u003c/em\u003e\u0026nbsp;\u003c/sub\u003e \u003cem\u003e@C][B\u003c/em\u003e \u003csub\u003e\u0026nbsp;\u003cem\u003e20\u003c/em\u003e\u0026nbsp;\u003c/sub\u003e \u003cem\u003eH\u003c/em\u003e \u003csub\u003e\u0026nbsp;\u003cem\u003e18\u003c/em\u003e\u0026nbsp;\u003c/sub\u003e \u003cem\u003e][Au(Ph\u003c/em\u003e \u003csub\u003e\u0026nbsp;\u003cem\u003e3\u003c/em\u003e\u0026nbsp;\u003c/sub\u003e \u003cem\u003eP)Cl]\u003c/em\u003e∙\u003cem\u003e0.5DMF (\u003c/em\u003e\u003cstrong\u003e1\u003c/strong\u003e\u003cem\u003e∙0.5DMF)\u003c/em\u003e\u003c/p\u003e\n \u003cp\u003eThe reaction proceeds in air at room temperature. A solution of [Au(Ph\u003csub\u003e3\u003c/sub\u003eP)Cl] (5 mmol, 2.45 g) in DMF (5 ml) was added to a solution of (Ph\u003csub\u003e4\u003c/sub\u003eP)\u003csub\u003e2\u003c/sub\u003e[B\u003csub\u003e20\u003c/sub\u003eH\u003csub\u003e18\u003c/sub\u003e] (0.5 mmol, 0.46 g) in DMF (10 ml) with stirring. The resulting colorless solution was allowed to stand in dark in air. After three days, the solution acquired the orange color. The formation of small light-orange crystals \u003cstrong\u003e1\u003c/strong\u003e\u0026middot;0.5DMF was observed after a week of standing in air. The crystals were filtered off and dried in air. Yield, 30% based on boron (0.59 g). \u003cstrong\u003eAnal. calcd.\u003c/strong\u003e for Au\u003csub\u003e8\u003c/sub\u003eC\u003csub\u003e145\u003c/sub\u003eH\u003csub\u003e138\u003c/sub\u003eP\u003csub\u003e8\u003c/sub\u003eCl\u003csub\u003eB20\u003c/sub\u003eP\u003csub\u003e8\u003c/sub\u003e: Au, 37.49; C, 41.43; H, 3.31; B, 5.14. Found, %: Au, 38.28; C 42.13; H 3.11; B 5.09. \u003cstrong\u003eIR\u003c/strong\u003e (NaCl, \u0026nu;, cm\u003csup\u003e\u0026ndash;1\u003c/sup\u003e): \u0026nu;(BH) 2541, 2522, 2503; \u0026delta;(ВВН) 998; \u0026nu;(CO)\u003csub\u003eDMF\u003c/sub\u003e 1674; 1584w, 1462, 1439, 1377, 1312w, 1179w, 1102, 748, 742, 723, 693. \u003cstrong\u003eNMR\u003c/strong\u003e \u003csup\u003e\u003cstrong\u003e11\u003c/strong\u003e\u003c/sup\u003e\u003cstrong\u003eB\u003c/strong\u003e (dmso-\u003cem\u003ed\u003c/em\u003e\u003csub\u003e6\u003c/sub\u003e, ppm): 31.59 (d, 2B\u003csub\u003eap\u003c/sub\u003e), 17.46 (s, 2B, B2, B2\u0026rsquo;), \u0026minus;\u0026thinsp;5.49 (d, 2B\u003csub\u003eeq\u003c/sub\u003e), \u0026minus;\u0026thinsp;11.15 (d, 4B\u003csub\u003eeq\u003c/sub\u003e), \u0026minus;\u0026thinsp;14.48 (d, 4B\u003csub\u003eeq\u003c/sub\u003e), \u0026minus;\u0026thinsp;18.07 (d, 4B), \u0026minus;\u0026thinsp;24.34 (d, 2B\u003csub\u003eap\u003c/sub\u003e). \u003cstrong\u003eNMR\u003c/strong\u003e \u003csup\u003e\u003cstrong\u003e31\u003c/strong\u003e\u003c/sup\u003e\u003cstrong\u003eP\u003c/strong\u003e (dmf-\u003cem\u003ed\u003c/em\u003e\u003csub\u003e\u003cem\u003e7\u003c/em\u003e\u003c/sub\u003e, ppm): 26.14 (s).\u003c/p\u003e\n \u003cp\u003eSingle crystal \u003cstrong\u003e1\u003c/strong\u003e∙0.5DMF suitable for X-ray diffraction study was taken directly from the reaction solution. Crystal data, details of data collection, and results of structure refinement are summarized in Table \u003cspan class=\"InternalRef\"\u003eS1\u003c/span\u003e. The crystallographic data were deposited with the Cambridge Crystallographic Data Center as supplementary publications under CCDC nos. 2126249. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ewww.ccdc.cam.ac.uk/structures\u003c/span\u003e\u003c/span\u003e.\u003c/p\u003e\n\u003c/div\u003e"},{"header":"RESULTS AND DISCUSSION","content":"\u003cp\u003eThe reaction between [B\u003csub\u003e20\u003c/sub\u003eH\u003csub\u003e18\u003c/sub\u003e]\u003csup\u003e2\u0026ndash;\u003c/sup\u003e and an excess of [Au(Ph\u003csub\u003e3\u003c/sub\u003eP)Cl] was performed in DMF. After a week, small light-orange crystals of complex [Au\u003csub\u003e7\u003c/sub\u003e(Ph\u003csub\u003e3\u003c/sub\u003eP)\u003csub\u003e7\u003c/sub\u003e@C][B\u003csub\u003e20\u003c/sub\u003eH\u003csub\u003e18\u003c/sub\u003e][Au(Ph\u003csub\u003e3\u003c/sub\u003eP)Cl]∙0.5DMF (\u003cb\u003e1\u003c/b\u003e∙0.5DMF) were isolated from the reaction solution according to the scheme.\u003c/p\u003e \u003cp\u003e[B\u003csub\u003e20\u003c/sub\u003eH\u003csub\u003e18\u003c/sub\u003e]\u003csup\u003e2\u0026ndash;\u003c/sup\u003e + 10 [Au(Ph\u003csub\u003e3\u003c/sub\u003eP)Cl][Au\u003csub\u003e7\u003c/sub\u003e(Ph\u003csub\u003e3\u003c/sub\u003eP)\u003csub\u003e7\u003c/sub\u003e@C][B\u003csub\u003e20\u003c/sub\u003eH\u003csub\u003e18\u003c/sub\u003e][Au(Ph\u003csub\u003e3\u003c/sub\u003eP)Cl]∙0.5DMF \u0026darr;\u003c/p\u003e \u003cp\u003eIn the IR spectrum of complex \u003cb\u003e1\u003c/b\u003e∙0.5DMF, a band with a maximum at 2522 cm\u003csup\u003e\u0026ndash;1\u003c/sup\u003e is observed, which related to the boron cluster anion acting as a counterion \u003csup\u003e[27\u0026ndash;30]\u003c/sup\u003e. A number of bands attributed to coordinated Ph\u003csub\u003e3\u003c/sub\u003eP molecule are also observed. DMF molecules give a band near 1600 cm\u003csup\u003e\u0026ndash;1\u003c/sup\u003e originated from ν(CO), which is clearly observed in the spectrum. X-ray diffraction pattern of crystals \u003cb\u003e1\u003c/b\u003e\u0026middot;0.5DMF, luminescence spectrum of crystals \u003cb\u003e1\u003c/b\u003e\u0026middot;0.5DMF, ESI MS spectrum of the reaction solution are shown in Figs. S4\u0026ndash;S6, respectively. Molecular view of compound \u003cb\u003e1\u003c/b\u003e\u0026middot;0.5DMF is shown in Fig. S7.\u003c/p\u003e \u003cp\u003eAccording to X-ray diffraction study, an asymmetric unit of \u003cb\u003e1\u003c/b\u003e∙0.5DMF contains the eicosaborate dianion [B\u003csub\u003e20\u003c/sub\u003eH\u003csub\u003e18\u003c/sub\u003e]\u003csup\u003e2\u0026ndash;\u003c/sup\u003e, a neutral [Au(Ph\u003csub\u003e3\u003c/sub\u003eP)Cl] complex, a [Au\u003csub\u003e7\u003c/sub\u003e(Ph\u003csub\u003e3\u003c/sub\u003eP)\u003csub\u003e7\u003c/sub\u003e@C]\u003csup\u003e2+\u003c/sup\u003e cation and one half solvent molecule (Fig. S7). Geometry of the linear [(Ph\u003csub\u003e3\u003c/sub\u003eP)AuCl] fragment is similar to that for AuCl\u0026middot;PPh\u003csub\u003e3\u003c/sub\u003e complex itself \u003csup\u003e[54]\u003c/sup\u003e and the boron cluster anion realizes the \u003cem\u003etrans\u003c/em\u003e-configuration (\u003cem\u003ecis\u003c/em\u003e, \u003cem\u003eiso\u003c/em\u003e, \u003cem\u003etrans\u003c/em\u003e and \u003cem\u003efac\u003c/em\u003e isomers of the [B\u003csub\u003e20\u003c/sub\u003eH\u003csub\u003e18\u003c/sub\u003e]\u003csup\u003e2\u0026ndash;\u003c/sup\u003e anion are discussed in review \u003csup\u003e[55]\u003c/sup\u003e). The cation is presented by unprecedented carbon-centered gold [Au\u003csub\u003e7\u003c/sub\u003e@C] cluster (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eEarlier a number of [Au\u003csub\u003e6\u003c/sub\u003e@C] octahedral clusters were synthesized \u003csup\u003e[56\u0026ndash;58]\u003c/sup\u003e. Silver and copper atoms are able to cap faces of these octahedra or their trigonal-prismatic isomers to form highly luminescent complexes \u003csup\u003e[46, 47, 59\u0026ndash;61]\u003c/sup\u003e. Clusters with hypercoordinated \u0026micro;\u003csub\u003e7\u003c/sub\u003e- and \u0026micro;\u003csub\u003e8\u003c/sub\u003e-carbon and boron atoms are also known, however, they are consist of up to 45 nickel atoms with additional copper, cobalt, or cadmium atoms \u003csup\u003e[62]\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eOverall geometry of the metal core in \u003cb\u003e1\u003c/b\u003e∙0.5DMF (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e) can be described as a capped trigonal prism, where the capping atom is situated above a square prism face. The Au\u0026hellip;Au distances and Au\u0026ndash;P and Au\u0026ndash;C bond lengths for this cluster as well as for previously reported [Au\u003csub\u003e6\u003c/sub\u003e(Ar\u003csub\u003e3\u003c/sub\u003eP)\u003csub\u003e6\u003c/sub\u003e@C] analogues are listed in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. Earlier described carbon-centered complexes include octahedral (OC) and trigonal-prismatic (TP) clusters. Both types can be capped with other group 11 metals (silver or copper). Geometry of the OC cluster remain nearly unchanged, for TP Ag\u003csub\u003e2\u003c/sub\u003e[Au\u003csub\u003e6\u003c/sub\u003e(Ar\u003csub\u003e3\u003c/sub\u003eP)\u003csub\u003e6\u003c/sub\u003e@C] \u003csup\u003e[60, 61]\u003c/sup\u003e and Cu\u003csub\u003e2\u003c/sub\u003e[Au\u003csub\u003e6\u003c/sub\u003e(Ar\u003csub\u003e3\u003c/sub\u003eP)\u003csub\u003e6\u003c/sub\u003e@C] \u003csup\u003e[47]\u003c/sup\u003e clusters the Au...Au distances are slightly shorter than those in OC ones. However, when the gold atom is added to OC cluster forming [Au\u003csub\u003e7\u003c/sub\u003e@C] it results in overall rearrangement of metal core into the capped trigonal prism with all Au...Au distances very close to each other and elongated Au\u0026ndash;C bonds. The carbon atom is only 0.053(3) \u0026Aring; shifted from the center of mass of seven gold atoms.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eSelected bond distances (\u0026Aring;) in carbon-centered gold clusters.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"6\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eCP\u003csup\u003ea\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eAu\u0026ndash;Au\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eP\u0026ndash;Au\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eAu\u0026ndash;C\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eReferences\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003e[Au\u003c/b\u003e\u003csub\u003e\u003cb\u003e7\u003c/b\u003e\u003c/sub\u003e\u003cb\u003e(Ph\u003c/b\u003e\u003csub\u003e\u003cb\u003e3\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eP)\u003c/b\u003e\u003csub\u003e\u003cb\u003e7\u003c/b\u003e\u003c/sub\u003e\u003cb\u003e@C]\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cb\u003eСTP\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e\u003cb\u003e2.7858(2)\u0026ndash;2.9970(2)\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e\u003cb\u003e2.2896(9)\u0026ndash;2.3158(9)\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e\u003cb\u003e2.226(3)\u0026ndash;2.359(4)\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e\u003cb\u003eThis work\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e[Au\u003csub\u003e6\u003c/sub\u003e(Ar\u003csub\u003e3\u003c/sub\u003eP)\u003csub\u003e6\u003c/sub\u003e@C]\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eOC\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e2.887\u0026ndash;3.226\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e2.02\u0026ndash;2.28\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e2.09\u0026ndash;2.15\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e[46, 47, 56, 58, 59, 63, 64, 44]\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAg\u003csub\u003e2\u003c/sub\u003e[Au\u003csub\u003e6\u003c/sub\u003e(Ar\u003csub\u003e3\u003c/sub\u003eP)\u003csub\u003e6\u003c/sub\u003e@C]\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eCOC\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e2.877\u0026ndash;3.176\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e2.250\u0026ndash;2.274\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e2.098\u0026ndash;2.145\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e[46, 57, 60, 61]\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAg\u003csub\u003e4\u003c/sub\u003e[Au\u003csub\u003e6\u003c/sub\u003e(Ar\u003csub\u003e3\u003c/sub\u003eP)\u003csub\u003e6\u003c/sub\u003e@C]\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eCOC\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e2.937\u0026ndash;3.052\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e2.265\u0026ndash;2.276\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e2.113\u0026ndash;2.118\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e[59]\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAg\u003csub\u003e6\u003c/sub\u003e[Au\u003csub\u003e6\u003c/sub\u003e(Ar\u003csub\u003e3\u003c/sub\u003eP)\u003csub\u003e6\u003c/sub\u003e@C]\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eCOC\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e2.914\u0026ndash;2.959\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e2.293\u0026ndash;2.303\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e2.14\u0026ndash;2.16\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e[59]\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAg\u003csub\u003e2\u003c/sub\u003e[Au\u003csub\u003e6\u003c/sub\u003e(Ar\u003csub\u003e3\u003c/sub\u003eP)\u003csub\u003e6\u003c/sub\u003e@C]\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eCTP\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e2.741\u0026ndash;2.903(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e2.260\u0026ndash;2.263\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e2.12\u0026ndash;2.26\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e[60, 61]\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCu\u003csub\u003e2\u003c/sub\u003e[Au\u003csub\u003e6\u003c/sub\u003e(Ar\u003csub\u003e3\u003c/sub\u003eP)\u003csub\u003e6\u003c/sub\u003e@C]\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eCTP\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e2.718\u0026ndash;2.867\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e2.252\u0026ndash;2.256\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e2.157\u0026ndash;2.168\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e[47]\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCu\u003csub\u003e2\u003c/sub\u003e[Au\u003csub\u003e6\u003c/sub\u003e(Ar\u003csub\u003e3\u003c/sub\u003eP)\u003csub\u003e6\u003c/sub\u003e@C]\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eCOC\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e2.921\u0026ndash;3.042\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e2.264\u0026ndash;2.270\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e2.108\u0026ndash;2.122\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e[47]\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003e \u003csup\u003ea\u003c/sup\u003e CP\u0026thinsp;=\u0026thinsp;coordination polyhedron: CTP is capped trigonal prism, OC is octahedron, COC is capped octahedron, CTP is capped trigonal prism.\u003c/p\u003e \u003cp\u003eWe assume that the central atom in the gold cluster is C. However, this fact cannot be stated unambiguously based on single-crystal X-ray diffraction data. We attempted to identify the central atom in the gold cluster by ESI mass-spectrometry. ESI MS spectra of complex \u003cb\u003e1\u003c/b\u003e is given in SI (Fig. S6). ESI MS spectrum recorded in the negative mode (Fig. S6b) clearly shows the presence of the boron cluster anion (as [B\u003csub\u003e20\u003c/sub\u003eH\u003csub\u003e17\u003c/sub\u003e]\u003csup\u003e\u0026ndash;\u003c/sup\u003e particles), products of its degradation ([B\u003csub\u003e10\u003c/sub\u003eH\u003csub\u003e9\u003c/sub\u003e]\u003csup\u003e\u0026ndash;\u003c/sup\u003e) and the associates of the boron cluster and cations (species Cat[An]\u003csup\u003e\u0026ndash;\u003c/sup\u003e, where Cat = [AuPh\u003csub\u003e3\u003c/sub\u003eP]\u003csup\u003e+\u003c/sup\u003e or Ph\u003csub\u003e4\u003c/sub\u003eP\u003csup\u003e+\u003c/sup\u003e; [An]\u003csup\u003e2\u0026ndash;\u003c/sup\u003e are B\u003csub\u003e10\u003c/sub\u003e or B\u003csub\u003e20\u003c/sub\u003e boron clusters. The [Au\u003csub\u003e7\u003c/sub\u003e@C]\u003csup\u003e2+\u003c/sup\u003e gold cluster highly likely degrades under ionization conditions giving smaller clusters [AuPh\u003csub\u003e3\u003c/sub\u003eP]\u003csup\u003e+\u003c/sup\u003e and [Au\u003csub\u003e2\u003c/sub\u003e(Ph\u003csub\u003e3\u003c/sub\u003eP)\u003csub\u003e2\u003c/sub\u003e]\u003csup\u003e+\u003c/sup\u003e, which were detected as Cat[An]\u003csup\u003e\u0026ndash;\u003c/sup\u003e ions. In the spectrum recorded in the positive mode (Fig. S6a) three main peaks are observed including the peaks of cations Ph\u003csub\u003e4\u003c/sub\u003eP\u003csup\u003e+\u003c/sup\u003e (\u003cem\u003em\u003c/em\u003e/\u003cem\u003ez\u003c/em\u003e\u0026thinsp;=\u0026thinsp;+\u0026thinsp;339.04), [Au(Ph\u003csub\u003e3\u003c/sub\u003eP)]\u003csup\u003e2+\u003c/sup\u003e (\u003cem\u003em\u003c/em\u003e/\u003cem\u003ez\u003c/em\u003e\u0026thinsp;=\u0026thinsp;+\u0026thinsp;228.93) and [Au\u003csub\u003e7\u003c/sub\u003e(Ph\u003csub\u003e3\u003c/sub\u003eP)\u003csub\u003e7\u003c/sub\u003eC][B\u003csub\u003e20\u003c/sub\u003eH\u003csub\u003e17\u003c/sub\u003e]\u003csup\u003e2+\u003c/sup\u003e (\u003cem\u003em\u003c/em\u003e/\u003cem\u003ez\u003c/em\u003e\u0026thinsp;=\u0026thinsp;+\u0026thinsp;1730.18). Nevertheless, we should note that there is the possibility that an oxygen or nitrogen atom is present in the center of the gold cluster but the carbon atom seems to be the most probable as concluded based on X-ray diffraction data. Unfortunately, we failed in our attempts to get high-quality \u003csup\u003e13\u003c/sup\u003eC NMR spectrum to prove the carbon atom in the center of the cluster because of insufficient solubility of the target compound in solvents.\u003c/p\u003e \u003cp\u003eIn contrast to the previously reported carbon-centered gold clusters \u003csup\u003e[46, 47, 59\u0026ndash;61]\u003c/sup\u003e, complex \u003cb\u003e1\u003c/b\u003e does not exhibit prominent luminescence (Fig. S5). It seems that the reason is the presence of the boron clusters in the compound. Note that the decrease in luminescence intensity was also observed for Zn(II) and Cd(II) benzimidazole complexes with [B\u003csub\u003e10\u003c/sub\u003eH\u003csub\u003e10\u003c/sub\u003e]\u003csup\u003e2\u0026ndash;\u003c/sup\u003e anions as compared to those with Cl\u003csup\u003e\u0026ndash;\u003c/sup\u003e and NO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026ndash;\u003c/sup\u003e anions \u003csup\u003e[8]\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eIt's also interesting to note that the charge balance in gold cluster [Au\u003csub\u003e7\u003c/sub\u003eL\u003csub\u003e7\u003c/sub\u003e@C]\u003csup\u003e2+\u003c/sup\u003e in compound \u003cb\u003e1\u003c/b\u003e is different from those of other C-centered clusters. Typically, the [Au\u003csub\u003e6\u003c/sub\u003eL\u003csub\u003e6\u003c/sub\u003e@C] unit carries a (+\u0026thinsp;2) charge resulting from six AuL\u003csup\u003e+\u003c/sup\u003e cations combined with a C\u003csup\u003e4\u0026ndash;\u003c/sup\u003e atom with 8 electrons. Thus, the [Au\u003csub\u003e7\u003c/sub\u003e(Ph\u003csub\u003e3\u003c/sub\u003eP)\u003csub\u003e7\u003c/sub\u003eC]\u003csup\u003e2+\u003c/sup\u003e unit seems to have an extra electron, which is highly likely a result of partial reduction by [B\u003csub\u003e20\u003c/sub\u003eH\u003csub\u003e18\u003c/sub\u003e]\u003csup\u003e2\u0026ndash;\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eUsually, special reagents are used to a desired central atom in the gold clusters. For example, tetrakis(dimethoxyboryl)methane C[B(OCH\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e]\u003csub\u003e4\u003c/sub\u003e was used to form [Au\u003csub\u003e6\u003c/sub\u003e(Ph\u003csub\u003e3\u003c/sub\u003eP)\u003csub\u003e6\u003c/sub\u003eC]\u003csup\u003e2+\u003c/sup\u003e from [Au(Ph\u003csub\u003e3\u003c/sub\u003eP)Cl] \u003csup\u003e[44]\u003c/sup\u003e. Herein we report un unprecedented one-pot synthesis to prepare seven-vertex gold cluster with a carbon atom in the center by self-assembly in the presence of the B\u003csub\u003e20\u003c/sub\u003e boron macropolyhedron.\u003c/p\u003e \u003cp\u003eWe believe that DMF is the source of the carbon atom formed as a result of DMF hydrolysis and further transformations of formic acid in the presence of boron clusters. DMF is known to degrade at various conditions giving carbon monoxide, methylamine, formaldehyde, formic acid \u003csup\u003e[65\u0026ndash;67]\u003c/sup\u003e. During years of research of boron cluster complexation, we have noted DMF transformations in the presence of metal salts. Particularly, formation of [B\u003csub\u003e10\u003c/sub\u003eH\u003csub\u003e9\u003c/sub\u003eOCHNMe\u003csub\u003e2\u003c/sub\u003e]\u003csup\u003e2\u0026ndash;\u003c/sup\u003e and [B\u003csub\u003e10\u003c/sub\u003eH\u003csub\u003e9\u003c/sub\u003eOH]\u003csup\u003e2\u0026ndash;\u003c/sup\u003e was observed in cobalt(II) and copper(II) complexation, respectively, with the [B\u003csub\u003e10\u003c/sub\u003eH\u003csub\u003e10\u003c/sub\u003e]\u003csup\u003e2\u0026ndash;\u003c/sup\u003e anion in DMF \u003csup\u003e[68, 69]\u003c/sup\u003e; DMF was the source of the substituent groups. In addition, the [Me\u003csub\u003e2\u003c/sub\u003eNH\u003csub\u003e2\u003c/sub\u003e]\u003csup\u003e+\u003c/sup\u003e cation was isolated as borate [Me\u003csub\u003e2\u003c/sub\u003eNH\u003csub\u003e2\u003c/sub\u003e][B\u003csub\u003e5\u003c/sub\u003eO\u003csub\u003e6\u003c/sub\u003e(OH)\u003csub\u003e4\u003c/sub\u003e] in silver(I) complexation with [B\u003csub\u003e11\u003c/sub\u003eH\u003csub\u003e14\u003c/sub\u003e]\u003csup\u003e\u0026ndash;\u003c/sup\u003e in DMF \u003csup\u003e[14]\u003c/sup\u003e. The listed examples confirm the possibility of deep transformations of DMF in the presence of boron cluster anions.\u003c/p\u003e \u003cp\u003eMoreover, when the studied reaction of [B\u003csub\u003e20\u003c/sub\u003eH\u003csub\u003e18\u003c/sub\u003e]\u003csup\u003e2\u0026ndash;\u003c/sup\u003e with 10 eq.\u0026nbsp;of [Au(Ph\u003csub\u003e3\u003c/sub\u003eP)Cl] was performed in CH\u003csub\u003e3\u003c/sub\u003eCN, C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e5\u003c/sub\u003eOH, 1,2-dichloromethane or N,N-dimethylsulfoxide, no color change for the reaction mixture was noted and the only gold-containing product isolated from the reaction mixtures was the initial [Au(Ph\u003csub\u003e3\u003c/sub\u003eP)Cl] complex. When C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e5\u003c/sub\u003eOH was used as the solvent, red-orange crystals precipitated, the parameters of which correspond to known gold cluster [Au\u003csub\u003e11\u003c/sub\u003e(PPh\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e7\u003c/sub\u003eCl\u003csub\u003e3\u003c/sub\u003e] [71], which is known to form from [Au(Ph\u003csub\u003e3\u003c/sub\u003eP)Cl]. Thus, we can conclude that the presence of DMF molecules is crucial to get the final cationic complex [Au\u003csub\u003e7\u003c/sub\u003e(Ph\u003csub\u003e3\u003c/sub\u003eP)\u003csub\u003e7\u003c/sub\u003e@C]\u003csup\u003e2+\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eIn general, in reactions between [Au(Ph\u003csub\u003e3\u003c/sub\u003eP)Cl] and boron clusters [B\u003csub\u003e10\u003c/sub\u003eH\u003csub\u003e10\u003c/sub\u003e]\u003csup\u003e2\u0026ndash; [33]\u003c/sup\u003e, [B\u003csub\u003e20\u003c/sub\u003eH\u003csub\u003e18\u003c/sub\u003e]\u003csup\u003e2\u0026ndash;\u003c/sup\u003e (this study), and [B\u003csub\u003e24\u003c/sub\u003eH\u003csub\u003e23\u003c/sub\u003e]\u003csup\u003e2\u0026ndash; [33]\u003c/sup\u003e there is a strong correlation between the size of the forming gold cluster and the size of the resulting boron cluster anion (see Figs. S1\u0026ndash;S3). The formed gold clusters consist of three, seven, and nine atoms, respectively, no matter if the [Au(Ph\u003csub\u003e3\u003c/sub\u003eP)Cl] : [boron cluster anion] ratio is 5 or 10. If the ratio is set to 1 : 1, then cation-anionic complex can be isolated as it was found for the reaction of [Ag\u003csub\u003e2\u003c/sub\u003e[B\u003csub\u003e12\u003c/sub\u003eH\u003csub\u003e12\u003c/sub\u003e]] with [Au(Ph\u003csub\u003e3\u003c/sub\u003eP)Cl], which gave ({Au(Ph\u003csub\u003e3\u003c/sub\u003eP)\u003csub\u003e2\u003c/sub\u003e}{Ag[B\u003csub\u003e12\u003c/sub\u003eH\u003csub\u003e12\u003c/sub\u003e]})\u003csub\u003e\u003cem\u003en\u003c/em\u003e\u003c/sub\u003e \u003csup\u003e[37]\u003c/sup\u003e. The formation of gold clusters in the presence of boron clusters can be explained by the tendency of gold(I) to form clusters in the presence of Ph\u003csub\u003e3\u003c/sub\u003eP and reducing agents; here, the boron cluster anions play the role of the reducing agents.\u003c/p\u003e \u003cp\u003eIn summary, the reaction of gold(I) complex [Au(PPh\u003csub\u003e3\u003c/sub\u003e)Cl] with the macropolyhedral boron anion [B\u003csub\u003e20\u003c/sub\u003eH\u003csub\u003e18\u003c/sub\u003e]\u003csup\u003e2\u0026ndash;\u003c/sup\u003e was studied in DMF. A novel cationic gold cluster [Au\u003csub\u003e7\u003c/sub\u003e(Ph\u003csub\u003e3\u003c/sub\u003eP)\u003csub\u003e7\u003c/sub\u003e@C]\u003csup\u003e2+\u003c/sup\u003e was isolated in one step and characterized as crystals [Au\u003csub\u003e7\u003c/sub\u003e(Ph\u003csub\u003e3\u003c/sub\u003eP)\u003csub\u003e7\u003c/sub\u003e@C][B\u003csub\u003e20\u003c/sub\u003eH\u003csub\u003e18\u003c/sub\u003e][Au(Ph\u003csub\u003e3\u003c/sub\u003eP)\u0026middot;0.5DMF. According to X-ray diffraction data, the gold cluster is found to be closely related to homo- and heterometallic [Au\u003csub\u003e6\u003c/sub\u003e(Ar\u003csub\u003e3\u003c/sub\u003eP)@C]\u003csup\u003e2+\u003c/sup\u003e clusters containing Group 11 metals and adopting \u0026micro;\u003csub\u003e6\u003c/sub\u003e-C ligand. DMF molecules are assumed to be the source of the central carbon atom.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003eACKNOWLEDGMENTS\u003c/p\u003e\n\u003cp\u003eThis work was supported by the Ministry of Science and Higher Education of the Russian Federation as part of the State Assignment of the Kurnakov Institute of General and Inorganic Chemistry RAS and the A.N. Nesmeyanov Institute of Organoelement Compounds RAS in the field of fundamental research. Single-crystal X-ray diffraction study was carried out at the Centre for Molecular Composition Studies of the A.N. Nesmeyanov Institute of Organoelement Compounds RAS. Powder X-ray diffraction study was performed at the Shared Research Center of the Kurnakov Institute of General and Inorganic Chemistry RAS.\u003c/p\u003e\n\u003cp\u003eThe authors thank Belousova O.N. (the Kurnakov Institute) for measurements and interpretation of the IR spectra.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eContributing roles\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eVVA\u0026nbsp;investigation, Writing - Original Draft;\u0026nbsp;AVV\u0026nbsp;Investigation, Writing - Review \u0026amp; Editing; VVN\u0026nbsp;Investigation, Data curation; GAB\u0026nbsp;Formal analysis, Visualization;\u0026nbsp;ЕАM\u0026nbsp;Conceptualization, Methodology;\u003csup\u003e\u0026nbsp;\u003c/sup\u003eNTK\u0026nbsp;Supervision.\u003c/p\u003e\n\u003cp\u003eEthical Approval\u003c/p\u003e\n\u003cp\u003eNot applicable.\u003c/p\u003e\n\u003cp\u003eFunding\u003c/p\u003e\n\u003cp\u003eThis work was supported by ongoing institutional funding. No additional grants to carry out or direct this particular research were obtained.\u003c/p\u003e\n\u003cp\u003eAvailability of data and materials\u003c/p\u003e\n\u003cp\u003eData available within the article or its supplementary materials\u003c/p\u003e\n\u003cp\u003eConflicts of interest. The authors declare that they have no conflicts of interest.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eElectronic Supplementary Information\u003c/strong\u003e. The online version contains supplementary material available at DOI. Supplementary material includes experimental details and supporting data (Figs. S1\u0026ndash;S7, Table S1).\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003e\u003cem\u003eBoron Science: New Technologies and Applications\u003c/em\u003e, Ed. N. S. Hosmane, CRC Press, 2012.\u003c/li\u003e\n\u003cli\u003eI.B. Sivaev, V.I. 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Chem. \u003cstrong\u003e2013\u003c/strong\u003e, 2002 (2013).\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"gold, complexation, boron cluster anions, gold clusters, X-ray diffraction","lastPublishedDoi":"10.21203/rs.3.rs-3935964/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-3935964/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"The reaction between [Au(Ph3P)Cl] and [B20H18]2– in DMF gave unprecedented heptanuclear cationic cluster [Au7(Ph3P)7@C]2+ isolated as [Au7(Ph3P)7@C][B20H18][Au(Ph3P)Cl]·0.5DMF in one step. The final compound was studied by 11B NMR and IR spectroscopies, ESI MS, single-crystal and powder X-ray diffractions. 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