HETEROATOM-FUNCTIONALIZED METHYLGOLD COMPLEXES - SYNTHESIS AND STRUCTURE OF CHLOROMETHYL(TRIPHENYLPHOSPHINE)GOLD AND PHENYLTHIOMETHYL(TRIMETHYLPHOSPHINE)GOLD

[AuCl(PPh3)] reacts with Mg(CH2Cl)Cl, prepared in situ from CH2ClI and iPrMgCl, in ether at -65 degrees C to give [Au(CH2Cl)(PPh3)] (la). la reacts with LiI, NaOMe and PPh3 to give [Au(CH2I)(PPh3)] (2), [Au(CH2 OMe)(PPh3)] (3) and [Au(CH2PPh3) (PPh3)]Cl (4), respectively. 2 decomp oses rapidly at room temperature, yielding ethylene and [AuI(PPh3)]. T he reaction of [AuCl(PMe3)] with LiCH2SPh in THF affords [Au(CH2SPh)(P Me3)] (5). The chloromethyl and the phenylthiomethyl complex la and 5 were isolated and characterized by NMR (H-1, C-13, P-31) spectroscopy as well as by single-crystal X-ray structure analysis. In the solid st ate discrete molecules of la and 5 are found with Linear C-Au-P units [C-Au-P 179,8(4)degrees (la), 179,1(1)degrees (5)]. The angle Au-C-Cl (115,4(6)degrees) in la is slightly greater than the tetrahedral angle .