Synthesis, crystal and molecular structure, spectroscopic and electrochemical studies of mu-oxo-bis{oxo-bis(4,6-dimethylpyrimidine-2-thiolate)rhenium(V)} complex

The dinuclear oxo-rhenium(V), mu-O[ReO(Me(2)pymS)(2)](2) species was prepar ed by the reaction of 4,6-dimerhylpyrimidine-2(1 H)-thione (Me(2)pymSH) wit h trans-[ReI2(EtO) (PPh3)(2)] or trans-[ReO(2)py(4)]Cl . 2H(2)O in differen t solvents. The compounds were characterized by elemental analysis, magneti c susceptibility, UV-VIS, IR and H-1 NMR spectroscopy and conductivity meas urements. Cyclic voltammetry shows that the mu-O[ReO(Me(2)pymS)(2)](2) spec ies, undergo a quasi-reversible single-electron process in which the oxygen -bridged dimeric framework is maintained. The structure of mu-O[ReO(Me(2)py mS)(2)](2) was determined by single-crystal X-ray diffraction methods. The dinuclear structure of [Re2O3(Me(2)pymS)(4)] compound consists of two [ReO( Me(2)pymS)(2)] moieties bridged by an oxygen atom. The backbone O-Re-O-Re=O is almost linear and each rhenium(V) ion lies in-the center of a distorted octahedron achieved through two deprotonated N,S-chelate ligands in the eq uatorial plane. (C) 1998 Elsevier Science Ltd. All rights reserved.