Sugimoto H, Suyama K, Sugimoto K, Miyake H, Takahashi I, Hirota S, Itoh S
A New Class of Sulfido/Oxo(dithiolene)-Molybdenum(IV) Complexes Derived from Sulfido/Oxo-Bis(tetrasulfido)molybdenum(IV) Anions. [JOURNAL ARTICLE]
Inorg Chem 2008 Oct 1.
Mono(dithiolene)sulfidomolybdenum(IV) complexes, [MoS(S 4)(bdt)] (2-) ( 2) and [MoS(S 4)(bdtCl 2)] (2-) ( 3) (1,2-benzenedithiolate = bdt, 3,6-dichloro-1,2-benzenedithiolate = bdtCl 2), were prepared by the substitution reaction of a tetrasulfido ligand in known [MoS(S 4) 2] (2-) ( 1) with the corresponding dithiol. Complexes 2 and 3 were irreversibly oxidized to give bis(mu-sulfido) dimolybdenum(V) species, {[MoS(bdt)] 2(mu-S) 2} (2-) ( 4) and {[MoS(bdtCl 2)] 2(mu-S) 2} (2-) ( 5), in aerobic acetonitrile. Mono(dithiolene)oxomolybdenum(IV) complexes, [MoO(S 4)(bdt)] (2-) ( 7) and [MoO(S 4)(bdtCl 2)] (2-) ( 8), that are oxo derivatives of 2 and 3 were also synthesized from a known [MoO(S 4) 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)(S 2C 2(COOMe) 2)] (2-) ( 9), and ligand substitution of the tetrasulfido group of 7 with bdt and bdtCl 2 yielded [MoO(bdt) 2] (2-) ( 10) and [MoO(bdt)(bdtCl 2)] (2-) ( 11), respectively. New sulfido/oxo molybdenum complexes were characterized by (1)H 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.
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