Synthesis and characterization of pentamethylcyclopentadienyl-rhodium(III) dialkyldithiophosphate complexes:: single-crystal structure of [Cp*RhCl{S2P(OEt)2}]

Reactions of [Cp*Rh(mu-Cl)Cl](2) with NH4S2P(OR)(2) in 1:1 and 1:2 stoichiometry gave complexes of the type [Cp*RhCl{S2P(OR)(2)}] (1) (Cp* = C5Me5; R = Et, Pr-n, Pr-i) and [Cp*Rh{S2P(OR)(2)}(2)] (2) (R = Et). Complex 1 on treatment with AgSO3CF3 in acetone followed by addition of a neutral donor ligand (L) gave cationic complexes, [Cp*Rh{S2P(OR)(2)}L][SO3CF3] (3) [R = Et; L = PPh3; P(C6H4Me-4)(3) = (Ptol(3)), AsPh3]. All the complexes 1-3 have been characterized by elemental analysis, electronic spectra, IR and NMR (H-1, P-31) data. The structure of one of the complexes, [Cp*RhCl{S2P(OEt)(2)}] (1a) has been established unambiguously by single-crystal X-ray analysis. The structure consists of a central rhodium atom coordinated to a eta(5)-pentamethylcyclopentadienyl ligand, a chelated dithiophosphate and a chloride ligand. (C) 1999 Elsevier Science S.A. All rights reserved.