Coordination chemistry of sulphines VI. Coordination of sulphines XYC=S=O (X,Y = aryl, S-aryl, Cl) to Pd0 and IrI complexes. Oxidative addition of the C-Cl side bond of (E)-(RS)ClC=S=O and (Z)-PhClC=S=O to Pd0

Abstract

The first Ir}I{-sulphine complex has been prepared by treating [Ir}I{Cl(cyclo-C{8}H{1}{4}){2}]{2} with fluorene-9-ylidine-sulphine, C{1}{2}H{8}C@?S@?O, in the presence of P(C{6}H{1}{1}){3} to give trans-[Ir}I{Cl{P(C{6}H{1}{1}){3}}{2}(C{1}{2}H{8}CSO)], in which the sulphine is @s-S coordinated. The complex [Pd}0{(PPh{3}){4}] reacts with the sulphines, (p-Me-C{6}H{4}S){2}C@?S@?O, (E)-(p-MeC{6}H{4}S)ClC@?S@?O, and (Z)-PhClC@?S@?O, to form the @h}2{-CS coordinated sulphine complexes [Pd}0{(PPh{3}){2}{(p-MeC{6}H{4}S){2}CSO}], [Pd}0{(PPh{3}){2}{(E)-(p-MeC{6}H{4}S)ClCSO}], and [Pd}0{(PPh{3}){2}{(Z)-PhClCSO}]. In solution [Pd}0{(PPh{3}){2}{(p-MeC{6}H{4}S){2}CSO}] does not undergo an oxidative addition reaction of the C@?S side bonds, but instead slow dissociation of the sulphine occurs. The complexes [Pd}0{(PPh{3}){2}{(E)-(p-MeC{6}H{4}S)ClCSO}] and [Pd}0{(PPh{3}){2}{(Z)-PhClCSO}] undergo in solution an oxidative addition of the C@?Cl side bonds yielding trans-(E)- and -(Z)-[Pd}I{}I{Cl(p-MeC{6}H{4}SCSO)(PPh{3}){2}] and trans-(E)- and -(Z)-[Pd}I{}I{Cl(PhCSO)(PPh{3}){2}], respectively. These reactions proceed at least in part via initially formed cis oxidative addition complexes, which subsequently rearrange to the trans products.