Abstract
Reaction of the new tridentate NS2 ligands 2-HSC6H4C(Me)NNHC(S)SCH2Ph (H2L1), 2-HSC6H4C(Me) NNHC(S)NHCPh3 (H2L2), 2-HSC6H4CHNNHC(S)NHCPh3 (H2L3) and 1-Ph-3-Me-5-HS-C3N2-CHNNC(SH)NHCPh3 (H2L4) with dioxomolybdenum(VI) precursors yielded mononuclear molybdenum(VI) complexes [MoO2(L1)(pic)] 1 (pic = 4-methylpyridine), [MoO2L2(MeOH)]·2.25 MeOH 2 and the dinuclear molybdenum(V) complexes [Mo2O3L32]·3CH2Cl2 3 and [Mo2O3L42] 4. The molecular structures of 1–3 were determined by single-crystal X-ray analysis. Complexes 1 and 2 each consist of a central cis-MoO2 unit with a mer co-ordinating tridentate dianionic ligand and one neutral donor molecule completing the octahedral environment of molybdenum(VI). Complex 3 exhibits an anti-Mo2O3 group co-ordinated by two mer chelating ligands. The symmetry-related molybdenum(V) centres are in a square pyramidal environment. Infrared, NMR and MS studies evidenced a comparable structure for 4. The reduction of the dioxomolybdenum(VI) compounds 1 and 2, achieved by addition of phosphines like PPh3, also leads to dinuclear µ-oxo-bridged complexes. The reverse oxidations of the oxomolybdenum(V) complexes are restricted by the nature of the ligand and the oxidizing agents.
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