A new series of bis(ene-1,2-dithiolato)tungsten(IV), -(V), -(VI) complexes as reaction centre models of tungsten enzymes: preparation, crystal structures and spectroscopic properties.

The carbomethoxy substituted dithiolene ligand (L(COOMe)) enabled us to develop a series of new bis(ene-1,2-dithiolato)tungsten complexes including W(IV)O, W(IV)(OSiBuPh(2)), W(VI)O(2), W(VI)O(OSiBuPh(2)) and W(VI)O(S) core structures. By using these tungsten complexes, a systematic study of the terminal monodentate ligand effects has been performed on the structural, spectroscopic properties and reactivity. The structure and spectroscopic properties of the tungsten complexes have also been compared to those of the molybdenum complexes coordinated by the same ligand to investigate the effects of the metal ion (W vs.

Oxo-sulfido- and oxo-selenido-molybdenum(VI) complexes possessing a dithiolene ligand related to the active sites of hydroxylases of molybdoenzymes: low temperature preparation and characterisation.

Oxo-sulfido- and oxo-selenido-molybdenum(VI) complexes with an ene-1,2-dithiolate ligand are generated as models of the active sites of molybdenum hydroxylases. The sulfide and selenide groups are highly reactive toward triphenylphosphine in the order of Se > S.

Monooxomolybdenum(VI) complexes possessing olefinic dithiolene ligands: probing Mo-S covalency contributions to electron transfer in dimethyl sulfoxide reductase family molybdoenzymes.

A monooxomolybdenum(VI) model complex for the oxidized active site in the DMSOR family of molybdoenzymes has been synthesized and structurally characterized. The compound was obtained from the desoxomolybdenum(IV) derivative by clean oxygen-atom transfer from an amine N-oxide in a manner similar to that observed in the enzyme. A combination of electronic absorption and resonance Raman spectroscopies, coupled with the results of bonding and excited-state calculations, has been used to provide strong support for a highly covalent Mo(d(xy))-S(dithiolene) pi*-bonding interaction in the molybdenum(VI) complex.

Dioxomolybdenum(VI) complexes with ene-1,2-dithiolate ligands: synthesis, spectroscopy, and oxygen atom transfer reactivity.

New dioxomolybdenum(VI) complexes, (Et(4)N)(Ph(4)P)[Mo(VI)O(2)(S(2)C(2)(CO(2)Me)(2))(bdt)] (2) and (Et(4)N)(Ph(4)P)[Mo(VI)O(2)(S(2)C(2)(CO(2)Me)(2))(bdtCl(2))](4)(S(2)C(2)(CO(2)Me)(2) = 1,2-dicarbomethoxyethylene-1,2-ditholate, bdt = 1,2-benzenedithiolate, bdtCl(2) = 3,6-dichloro-1,2-benzenedithiolate), that possess at least one ene-1,2-dithiolate ligand were synthesized by the reaction of their mono-oxo-molybdenum(IV) derivatives, (Et(4)N)(2)[Mo(IV)O(S(2)C(2)(CO(2)Me)(2))(bdt)] (1) and (Et(4)N)(2)[Mo(IV)O(S(2)C(2)(CO(2)Me)(2))(bdtCl(2))] (3), with Me(3)NO. Additionally, the bis(ene-1,2-dithiolate)Mo(VI)O(2) complex, (Et(4)N)(Ph(4)P)[Mo(VI)O(2)(S(2)C(2)(CO(2)Me)(2))(2)] (6), was isolated. Complexes 2, 4, and 6 were characterized by elemental analysis, negative-ion ESI mass spectrometry, and IR spectroscopy.