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 d isu I phide with d i -7-cyclopentadienylva nadium (I I), en neacarbo nyldii ron (0) , potassium pentacyanocobaltate(il), and cyclo-octa-l,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, interalia, by infrared (i.r.), and for (n-C5H5),VCS2, by electron spin resonance (e.s.r.) spectra.The interaction of tris(triphenylphosphine)chlororhodium(l) with carbon disulphide in presence of excess of triphenylphosphine and methanol, produces the first example of a thiocarbonyl (CS) complex, trans-bis(tripheny1phosphine)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.( a ) A I .

The dimerisation of carbon disulfide on Fe centres. Some new tetrathiolene complexes of iron

“…It could not be purified as it decomposed rapidly both in the solid state and solution. However, 3a is stable in solution in the presence of CO before the addition of [Ph 3 C]BF 4 (above) and it is for this solution or a similar one in CDCl 3 that the following spectroscopic data were obtained: IR ν/cm Ϫ1 (relative peak heights): ν(CO), 2017 (10) (20,600).…”

“…Published methods or extensions thereof were used to prepare [Fe 2 (CO) 9 ], 9 and [Fe(L) 2 (CO) 2 (η 2 -CS 2 )] where L is a P() † Tetrathiolene is used to differentiate the MS 2 C 2 S 2 M complexes from the dithiolene complexes R 2 C 2 S 2 M. ligand. 1, 10 Other chemicals were purchased and used as received. Reactions were carried out in dried and deoxygenated solvents under an atmosphere of nitrogen at room temperature unless stated otherwise.…”

The photochemical generation of heterobimetallic complexes containing carbon disulfide

“…spectral data with those reported previously for 3b. 8 The trans stereochemistry of 3a and 3b was evident from the 1 H NMR parameters (see below). The disulfide products are formed in high yields, this being a marked improvement on the conventional synthetic routes of either refluxing [Fe 2 (CO) 9 ] and tertiary phosphine in CS 2 as the solvent 8,9 or ligand exchange reactions.…”

Carbon

“…CS 2 complexes of vanadium, iron, cobalt, ruthenium and iridium have also been prepared 267 ; the interaction of tris(triphenylphosphine)dichlororuthenium(II) with CS 2 268 leads to two complexes, [RuCl(CS 2 )(PPh 3 ) 3 ]Cl and [RuCl(CS)(PPh 3 ) 2 ] 2 , containing the thiocarbonyl group. Carbon disulphide with tris(triphenylphosphine)platinum(0) gives the stable adduct (Ph 3 P) 2 PtCS 2 in which CS 2 retains a planar configuration.…”