Abstract

Reactions of complexes [{(?5-C5Me5)MCl2}2] (M = Rh, Ir) with the ligand (MeS)2CH2 in CH2Cl2 solution led to the neutral dinuclear complexes of the general formula [{(?5-C5Me5)MCl2} 2{?-(MeS)2CH2}] [M = Rh (1), Ir (2)]. Compound 1 reacts in CH2Cl2 solution with silver tetrafluoroborate in 1:2 molar ratio to yield the dinuclear cationic complex [{(?)5-C5Me5)Rh}2(?- Cl)2{?-(MeS)2CH2}](BF4) 2·H2O (3). Compound 2 reacts with silver salts in analogous conditions to give the mononuclear cationic complex [(?5-C5Me5)IrCl{? 2-(MeS)2CH2}]BF4 (4). Reactions of the starting complexes [{(?5-C5Me5)MCl2}2] with the ligand (PhS)2CH2 afforded the mononuclear complexes [(?5-C5Me5)MCl2(? 1-(PhS)2CH2)] [M = Rh (5), Ir (6)]. All the complexes have been characterised by analytical and spectroscopic means, and the fluxional behaviour of 4, in solution, has been studied. The crystal structures of complexes 3 and 6 have been established by X-ray crystallography. Complex 3 crystallised in space group P21/n, a =11.848(2), b = 12.693(2), c = 21.608(4) Å, Z = 95.18(2)° and Z = 4. The complex cation consists of two (?5-C5Me5)Rh moieties connected by two chloride atoms and one dithioether group. The two rhodium atoms are separated by 3.6093(10) Å. Complex 6 crystallised in space group P21/c, a = 8.366(1), b = 16.011(3), c = 17.911(2) Å, ?= 100.28(1)° and Z = 4. The iridium atom has a distorted octahedral co-ordination with a ?5-C5Me5 group occupying the centre of three octahedral sites, two chloride atoms and a sulphur of a monodentate bis(phenylthio)methane ligand. © 2001 Elsevier Science B.V. All rights reserved.