Carbon disulphide, carbonyl sulphide, and alkyl and aryl isothiocyanate and perfluorothioacetone complexes of nickel, palladium, platinum, rhodium, and iridium

Abstract

The interaction of carbon disulphide with triphenylphosphine complexes of Ni, Pd, Pt, Rh, and Ir in zero or +1 oxidation states leads to complexes in which the CS₂ ligand is “π-bonded”, as exemplified by the first member of this new class of compound whose structure has been confirmed by crystallographic methods, bis(triphenylphosphine)(carbon disulphide)platinum(II). Evidence for a donor complex of CS₂ has been obtained in one case. Structurally related “π-complexes” have been obtained from carbonyl sulphide, and alkyl and aryl isothiocyanates. An allyl isothiocyanate–platinum complex is best formulated with metal-bonded π-allyl and thiocyanato-groups, however. In the interaction of the isothiocyanates with tris(triphenylphosphine)chlororhodium(I), both “π-bonded” and donor co-ordinated isothiocyanates are present. A π-perfluorothioacetone complex (Ph₃P)₂Pt(C₂F₆CS) and a benzoyl complex (Ph₃P)₂PtCl(COPh) are obtained from the interaction of Pt(PPh₃)₃ with 2,2,4,4-tetrakis(trifluoromethyl)-1,3-dithietan and benzoyl chloride, respectively; also described is the arylazo-complex RhCl₂(p-FC₆H₄N₂)(PPh₃)₂, 0·5CHCl₃, obtained by interaction of para-fluorophenyldiazonium tetrafluoroborate with RhCl₂H(PPh₃)₂.