Molybdenum(VI) complexes of the type Mo(NAr)(sma)(L) (Ar= 2,6-diisopropylphenyl; sma = N-salicylidene-2-amidothiophenolate; L = catecholate, 1; 2-mercaptophenolate, 2; 1,2-benzenedithiolate, 3) have been shown to have reversible electrochemical one-electron reductions. In order to further characterize the resulting Mo(V) complexes, we chemically reduced the molybdenum(VI) complexes with cobaltocene to isolate light brown solids of the type [CoCp2][MoV(NAr)(sma)(L)]. All three Mo(V) imido complexes displayed EPR signals (1: g0 = 1.932, AMo = 48 G; 2: g0 = 1.970, AMo = 44 G, AN = 3 G; 3: g0 = 1.970, AMo = 40 G, AN= 3 G). Broadened peaks were observed in the 1H NMR spectra of each Mo(V) complex which is consistent with paramagnetic species. X-ray crystallographic data revealed that the cyclopentaldienyl rings in the colbatocenium cation occupy an eclipsed structure in contract to the staggered structure observed in cobaltocene.

Synthesis and characterization of new molybdenum(V) complexes with N-salicylidene-2-aminothiophenol

251st National Meeting (2016)

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