Phosphoniothiolat–Komplexe: Darstellung und Umlagerung in Phosphan–Komplexe

Abstract

Phosphoniothiolate Complexes: Synthesis and Rearrangement to Phosphane ComplexesPentacarbonyl(thiobenzaldehyde)tungsten (1) reacts with phosphanes PR3 to give the phosphoniothiolate / complexes (CO)5W[SC(H)Ph(PR3)] (2) (RMe, Et, Ph, 4–MeC6H4). Similarly, the thiobenzophenone complex (CO)5W[SCPh2] (3) affords (CO)5W[SC(Ph)2PMe3] (4). The phosphoniothiolate complexes obtained from 1 and PPh2H or P(2,4,6–Me3C6H2)H2 rapidly rearrange by formal S,P migration of (CO)5W and P,C migration of H to form the phosphate complexes (CO)5W{P‐(Ph)2[C(Ph)H(SH)]} (5) and (CO)5W{P(2,4,6–Me3C6H2)H‐[C(Ph)H(SH)]} (6/6′).