Heteroatomfunktionalisierte Methylgold-Komplexe: Synthese und Struktur von Chlormethyl(triphenylphosphin)- und Phenylthiomethyl(trimethylphosphin)gold

Heteroatom-functionalized Methylgold Complexes: Synthesis and Structure of Chloromethyl(triphenylphosphine)- and Phenylthiomethyl(trimethylphosphine)gold [AuCl(PPh₃)] reacts with Mg(CH₂Cl)Cl, prepared in situ from CH₂ClI and iPrMgCl, in ether at –65 °C to give [Au(CH₂Cl)(PPh₃)] ( 1 a ). 1 a reacts with LiI, NaOMe and PPh₃ to give [Au(CH₂I)(PPh₃)] ( 2 ), [Au(CH₂OMe)(PPh₃)] ( 3 ) and [Au(CH₂PPh₃)(PPh₃)]Cl ( 4 ), respectively. 2 decomposes rapidly at room temperature, yielding ethylene and [AuI(PPh₃)]. The reaction of [AuCl(PMe₃)] with LiCH₂SPh in THF affords [Au(CH₂SPh)(PMe₃)] ( 5 ). The chloromethyl and the phenylthiomethyl complex 1 a and 5 were isolated and characterized by NMR (¹H, ¹³C, ³¹P) spectroscopy as well as by single-crystal X-ray structure analysis. In the solid state discrete molecules of 1 a and 5 are found with linear C–Au–P units [C–Au–P 179,8(4)° ( 1 a ), 179,1(1)° ( 5 )]. The angle Au–C–Cl (115,4(6)°) in 1 a is slightly greater than the tetrahedral angle.