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A New Class of Sulfido/Oxo(dithiolene)−Molybdenum(IV) Complexes Derived from Sulfido/Oxo-Bis(tetrasulfido)molybdenum(IV) Anions

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journal contribution
posted on 03.11.2008, 00:00 by Hideki Sugimoto, Koichiro Suyama, Kunihisa Sugimoto, Hiroyuki Miyake, Isao Takahashi, Shun Hirota, Shinobu Itoh
Mono(dithiolene)sulfidomolybdenum(IV) complexes, [MoS(S4)(bdt)]2− (2) and [MoS(S4)(bdtCl2)]2− (3) (1,2-benzenedithiolate = bdt, 3,6-dichloro-1,2-benzenedithiolate = bdtCl2), were prepared by the substitution reaction of a tetrasulfido ligand in known [MoS(S4)2]2− (1) with the corresponding dithiol. Complexes 2 and 3 were irreversibly oxidized to give bis(μ-sulfido) dimolybdenum(V) species, {[MoS(bdt)]2(μ-S)2}2− (4) and {[MoS(bdtCl2)]2(μ-S)2}2− (5), in aerobic acetonitrile. Mono(dithiolene)oxomolybdenum(IV) complexes, [MoO(S4)(bdt)]2− (7) and [MoO(S4)(bdtCl2)]2− (8), that are oxo derivatives of 2 and 3 were also synthesized from a known [MoO(S4)2]2− (6) of an oxo derivative of 1 and the corresponding dithiol. Further, the electrophilic addition of dimethyl acetylenedicarboxylate to 7 gave [MoO(bdt)(S2C2(COOMe)2)]2− (9), and ligand substitution of the tetrasulfido group of 7 with bdt and bdtCl2 yielded [MoO(bdt)2]2− (10) and [MoO(bdt)(bdtCl2)]2− (11), respectively. New sulfido/oxo molybdenum complexes were characterized by 1H NMR, IR, ESI-MS, Raman, and UV−vis spectroscopies; cyclic voltammetry; and elemental analysis, and crystal structures of 2, 3, 5, 7, and 8 were determined by X-ray analysis.