Dithioethers as ligands in pentamethylcyclopentadienylrhodium(III) and iridium(III) complexes. Crystal structures of [{(#eta#~5-C_5Me_5)Rh}_2(#mU#-Cl)_2{#mu#-(MeS)_2CH_2}](BF_4)_2.H_2O and [(#eta#~5-C_5Me_5)IrCl_2{#eta#~1-(PhS)_2CH_2}]

摘要

Reactions of complexes [{(115-C5Me5)MCIJ~ (M = Rh, Ir) with the ligand (MeS)2CH~ in CH2CI2 solution led to the neutral dinuclear complexes of the general formula [{(1l5-C5Me5)MCI2}2{~-(MeS)2CH2}] [M = Rh (I), Ir (2)]. Compound I reacts in CH2CI2 solution with silver tetrafluoroborate in 1:2 molar ratio to yield the dinuclear cationic complex [{(1l5-C5Me5)Rh}2(~. CI)2{~-(MeS)2CH2}](BF4)2.H2O (3). Compound 2 reacts with silver salts in analogous conditions to give the mononuclear cationic complex [(1l5-C5Me5)IrCI{1l2-(MeS)2CH2}]BF4 (4). Reactions of the starting complexes [{(1l5-CsMes)MCI2}~ with the ligand (PhS)2CH2 afforded the mononuclear complexes [(1ls-CsMes)MCI2(1l'-(PhS)2CH~] [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 P2,, a = 11.848(2), b = 12.693(2), c = 21.608(4) A, p = 95.18(2)0 and Z = 4. The complex cation consists of two (1ls-CsMes)Rh moieties connected by two chloride atoms and one dithioether group. The two rhodium atoms are separated by 3.6093(10) A. Complex 6 crystallised in space group P21/c, a = 8.366(1), b = 16.011(3), c = 17.911(2) A, p = 100.28(1)0 and Z = 4. The iridium atom has a distorted octahedral co-ordination with a1ls.CsMes group occupying the centre of three octahedral sites, two chloride atoms and a sulphur of a monodenta;te bis(phenylthio )methane ligand.