Oxidation of trans-[RhCl(CO)(PPh2R)2] (R = Et, Pri, CH2SPh) with HgCl2 to form rhodium–mercury bonded complexes, and complexes of mercury(II) with phosphinoalkylthioethers or dithioethers

Abstract

Mononuclear complexes of HgII of 1:1 stoicheiometry are formed with the chelating ligands Ph2P(CH2)nSPh (n = 1, 2) or (PhS)2(CH2)n (n = 1–4). In contrast to the behaviour of trans-[RhCl(CO)(PPh3)2], reactions of trans-[RhCl(CO)(PPh2R)2] (R = Et, Pri, or CH2SPh) with HgCl2 give the corresponding oxidative addition complexes [RhCl2(HgCl)(CO)(PPh2R)2].•For [RhCl2(HgCl)(CO)(PPh2CH2SPh)2] the pendant thioether groups coordinate to mercury. Reactions of HgCl2 with [MCl2(Ph2PCH2SPh)2] (M = Pd, Pt) give the corresponding heterodinuclear, Ph2PCH2SPh bridged complexes, [MHgCl4(μ-Ph2PCH2SPh)2]. The 199Hg nmr spectrum of [RhCl2(HgCl)(CO)(PEtPh2)2] has been obtained, and the first value for 1J(103Rh—199Hg) has been measured.