Carbon disulphide complexes of vanadium, iron, cobalt, ruthenium, and iridium; the preparation of trans-bis(triphenylphosphine)thiocarbonylhalogeno-rhodium(I) and -rhodium(III) complexes

Abstract

The interaction of carbon disulphide with di-π-cyclopentadienylvanadium(II), enneacarbonyldi-iron(0), potassium pentacyanocobaltate(II), and cyclo-octa-1,5-dienechloroiridium(I) leads to complexes where carbon disulphide is co-ordinated to the metal by both carbon and sulphur atoms or, in the cobalt complex, as a bridge group –Co–SC(S)Co–. The complexes are characterised, inter alia, by infrared (i.r.), and for (π-C₅H₅)₂VCS₂, by electron spin resonance (e.s.r.) spectra.

The interaction of tris(triphenylphosphine)chlororhodium(I) with carbon disulphide in presence of excess of triphenylphosphine and methanol, produces the first example of a thiocarbonyl (CS) complex, trans-bis(triphenylphosphine)thiocarbonylchlororhodium(I). This complex and the corresponding bromide can be oxidised by halogen to the octahedral complexes RhX₃(CS)(PPh₃)₂. The mode of formation of the thiocarbonyl complex is discussed briefly.