Osmium nitrosyl complexes with osmium-tin bonds crystal structure of Os[Sn(p-tolyl)3](NO)(CO)2(PPh3)

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Abstract Oxidative addition of the tin-hydride bond of (p-tolyl)3SnH to the formal osmium(0) nitrosyl complexes, OsCl(NO)(PPh3)3 and “OsH(NO)(PPh3)2”, affords the osmium(II) stannyl complexes, Os[Sn(p-tolyl)3]HCl(NO)(PPh3)2 (1), and Os[Sn(p-tolyl)3]H2(NO)PPh3)2 (2) respectively. “OsH(NO)(PPh3)2” was generated in situ by thermal elimination of H2 from OsH3(NO)(PPh3)2 (5). It was established from 1H and 31P NMR evidence that 1 has two cis phosphine ligands, one of which is trans to the hydride ligand and the other trans to the stannyl ligand. The high trans influence of the hydride ligands confers lability on one phosphine ligand, which can be readily replaced by reaction with sodium dimethyldithiocarbamate forming OsH[Sn(p-tolyl)3](S2CNMe2)(NO)(PPh3) (3), and reaction with carbon monoxide gives eventually, after displacement of one triphenylphosphine and loss of HCl, Os[Sn(p-tolyl)3](NO)(CO)2(PPh3) (4), a formal osmium(O) stannyl complex. The crystal structure of this five-coordinate osmium-tin complex, 4, has been determined.