Structures and properties of complexes MCl(C5Me5)(N-S)(PF6), M = Rh, Ir, with N-S = 1-methyl-2-(alkylthiomethyl)-1H-benzimidazole ligands

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Journal of Organometallic Chemistry, 596 (1-2): 84--89 (2000)
DOI: 10.1016/S0022-328X(99)00544-6


The four complexes MCl(C5Me5)(N-S)(PF6), M = Rh, Ir; N-S = 1-methyl-2-(methylthiomethyl)-1H-benzimidazole (mmb) and 1-methyl-2-(tert-butylthiomethyl)-1H-benzimidazole (mtb) were synthesized and characterized by spectroscopy, electrochem. and x-ray crystallog. (as MeOH solvates). The essential coordination features, viz., longer M-S ($\sim$2.38 A) and shorter M-N bonds ($\sim$2.09 A) in five-membered chelate rings are common to all four species. Cyclic voltammetry reveals irreversible two-electron redn. to MI complexes and partially reversible oxidn. to IrIV species for IrCl(C5Me5)(mtb)+. The results are discussed in comparison with those obtained for a-diimine (N-N) complexes of the MCl(C5Me5)+ fragments. on SciFinder(R)



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