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We are currently investigating the coordination chemistry and ligand properties of the dianionic stanna-closo-dodecaborate cluster [SnB 11 H 11 ] 2À (1). So far, in a variety of transition-metal complexes, the ligand was found to coordinate exclusively as a terminal ligand with the formation of a tin-metal bond.[1]Here we present the surprising results of preliminary investigations on the stannaborate chemistry with gold electrophiles. 2À :[(Ph 3 P)AuCl]). Interestingly, 50 % of the starting material [(Ph 3 P)AuCl] is still present in the mixture. The other signals in the 31 P NMR spectrum exhibit tin satellites, which provides direct spectroscopic evidence for the formation of a covalent Au À Sn bond. In this solution the anion of 3 is the major Au-Sn component (35 %) and exhibits a characteristic signal in the 31 P NMR spectrum at d = 54.4 ppm with a 2 J(Sn,P) coupling constant of 109.4 Hz. The anion of 2 was identified in solution by a small signal (3 %) at d = 62.9 ppm ( 2 J(Sn,P) = 186.9 Hz). A bis(triphenylphosphane) substitution product ([(Ph 3 P) 2 Au(SnB 11 H 11 )] À ) is also present in solution (5 %) and displays a signal in the 31 P NMR spectrum at d = 44.5 ppm ( 2 J(P, 117 Sn) = 984.2 Hz, 2 J(P, 119 Sn) = 1027.5 Hz). This compound was synthesized in a separate experiment from nucleophile 1, PPh 3 , and [(Ph 3 P)AuCl] in reasonable yield and details will be published later. Treatment of the [(Ph 3 P)AuCl] with 1.5 equivalents of heteroborate 1, led to an increase in the amount of Au 2 Sn 3 cluster 3 formed (68.6 % yield).The geometry of the metal core in the anions of 2 (Figure 1) and 3 (Figure 2)
We are currently investigating the coordination chemistry and ligand properties of the dianionic stanna-closo-dodecaborate cluster [SnB 11 H 11 ] 2À (1). So far, in a variety of transition-metal complexes, the ligand was found to coordinate exclusively as a terminal ligand with the formation of a tin-metal bond.[1]Here we present the surprising results of preliminary investigations on the stannaborate chemistry with gold electrophiles. 2À :[(Ph 3 P)AuCl]). Interestingly, 50 % of the starting material [(Ph 3 P)AuCl] is still present in the mixture. The other signals in the 31 P NMR spectrum exhibit tin satellites, which provides direct spectroscopic evidence for the formation of a covalent Au À Sn bond. In this solution the anion of 3 is the major Au-Sn component (35 %) and exhibits a characteristic signal in the 31 P NMR spectrum at d = 54.4 ppm with a 2 J(Sn,P) coupling constant of 109.4 Hz. The anion of 2 was identified in solution by a small signal (3 %) at d = 62.9 ppm ( 2 J(Sn,P) = 186.9 Hz). A bis(triphenylphosphane) substitution product ([(Ph 3 P) 2 Au(SnB 11 H 11 )] À ) is also present in solution (5 %) and displays a signal in the 31 P NMR spectrum at d = 44.5 ppm ( 2 J(P, 117 Sn) = 984.2 Hz, 2 J(P, 119 Sn) = 1027.5 Hz). This compound was synthesized in a separate experiment from nucleophile 1, PPh 3 , and [(Ph 3 P)AuCl] in reasonable yield and details will be published later. Treatment of the [(Ph 3 P)AuCl] with 1.5 equivalents of heteroborate 1, led to an increase in the amount of Au 2 Sn 3 cluster 3 formed (68.6 % yield).The geometry of the metal core in the anions of 2 (Figure 1) and 3 (Figure 2)
We are currently investigating the coordination chemistry and ligand properties of the dianionic stanna-closo-dodecaborate cluster [SnB 11 H 11 ] 2À (1). So far, in a variety of transition-metal complexes, the ligand was found to coordinate exclusively as a terminal ligand with the formation of a tin-metal bond.[1]Here we present the surprising results of preliminary investigations on the stannaborate chemistry with gold electrophiles. 2À :[(Ph 3 P)AuCl]). Interestingly, 50 % of the starting material [(Ph 3 P)AuCl] is still present in the mixture. The other signals in the 31 P NMR spectrum exhibit tin satellites, which provides direct spectroscopic evidence for the formation of a covalent Au À Sn bond. In this solution the anion of 3 is the major Au-Sn component (35 %) and exhibits a characteristic signal in the 31 P NMR spectrum at d = 54.4 ppm with a 2 J(Sn,P) coupling constant of 109.4 Hz. The anion of 2 was identified in solution by a small signal (3 %) at d = 62.9 ppm ( 2 J(Sn,P) = 186.9 Hz). A bis(triphenylphosphane) substitution product ([(Ph 3 P) 2 Au(SnB 11 H 11 )] À ) is also present in solution (5 %) and displays a signal in the 31 P NMR spectrum at d = 44.5 ppm ( 2 J(P, 117 Sn) = 984.2 Hz, 2 J(P, 119 Sn) = 1027.5 Hz). This compound was synthesized in a separate experiment from nucleophile 1, PPh 3 , and [(Ph 3 P)AuCl] in reasonable yield and details will be published later. Treatment of the [(Ph 3 P)AuCl] with 1.5 equivalents of heteroborate 1, led to an increase in the amount of Au 2 Sn 3 cluster 3 formed (68.6 % yield).The geometry of the metal core in the anions of 2 (Figure 1) and 3 (Figure 2)
The reaction of aminotributylstannane or aminotrimethylstannane derivatives with the dihydride of decacarbonyltriosmium in ether−hexane solution (5:1) at room temperature affords the heterometallic clusters [(μ-H)Os3(CO)10(HE)(SnR3)] (1−8) (HE = dimethylamine (1, 5), pyrrolidine (2, 6), piperidine (3, 7), and morpholine (4, 8)) and the α-carbon−hydrogen bond activation of the secondary amine moiety of (2) (2a) in low yield. In all these heterometallic clusters the secondary amine ligand occupies a weak axial coordination site on the osmium triangle, eventually stabilized through the formation of intramolecular hydrogen-bonding interaction between the N−H and the axial carbonyl ligands. The stannyl ligand (SnBu3 or SnMe3) occupies an equatorial position on the osmium triangle, as expected for a bulky substituent. The metal carbonyl angles open out and the Os−C−O axes deviate from linearity so as to bring the carbonyl moieties closer to the tin atom in an “umbrella effect”, for 3, 5, 6, 7, 7‘, 8, and 2a. We were unable to grow single crystals for the compounds 1, 2, and 4. However, the spectroscopic information (1H, 13C, and 119Sn NMR) is similar for compounds 1−8 and 2a. Thus, it is assumed that they should present similar interactions in the triosmium cluster. All the compounds were characterized by IR, 1H, 13C, and 119Sn NMR, mass spectra, and elemental analysis. Solid-state structures of 3, 5, 6, 7, 7‘, 8, and 2a were established by single-crystal X-ray diffraction analyses.
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