Dioxo-Molybdenum(VI) and Mono-oxo-Molybdenum(IV) Complexes Supported by New Aliphatic Dithiolene Ligands: New Models with Weakened Mo=O Bond Characters for the Arsenite Oxidase Active Site
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- 作者：Hideki Sugimoto ; Makoto Harihara ; Motoo Shiro ; Kunihisa Sugimoto ; Koji Tanaka ; Hiroyuki Miyake ; and Hiroshi Tsukube
- 刊名：Inorganic Chemistry
- 出版年：2005
- 出版时间：September 5, 2005
- 年：2005
- 卷：44
- 期：18
- 页码：6386 - 6392
- 全文大小：119K
- 年卷期：v.44,no.18(September 5, 2005)
- ISSN：1520-510X
文摘
The cis-dioxo-molybdenum(VI) complexes, [MoO2(LH)2]2- (1b), [MoO2(LS)2]2- (2b), and [MoO2(LO)2]2- (3b) (LH =cyclohexene-1,2-dithiolate, LS = 2,3-dihydro-2H-thiopyran-4,5-dithiolate, and LO = 2,3-dihydro-2H-pyran-4,5-dithiolate),with new aliphatic dithiolene ligands were prepared and investigated by infrared (IR) and UV-vis spectroscopicand electrochemical methods. The mono-oxo-molybdenum(IV) complexes, [MoO(LH)2]2- (1a), [MoO(LS)2]2- (2a),and [MoO(LO)2]2- (3a), were further characterized by X-ray crystal structural determinations. The IR and resonanceRaman spectroscopic studies suggested that these cis-dioxo molybdenum(VI) complexes (1b-3b) had weakerMo=O bonds than the common MoVIO2 complexes. Complexes 1b-3b also exhibited strong absorption bands inthe visible regions assigned as charge-transfer bands from the dithiolene ligands to the cis-MoO2 cores. Becausethe oxygen atoms of the cis-MoVIO2 cores are relatively nucleophilic, these complexes were unstable in proticsolvents and protonation might occur to produce MoVIO(OH), as observed with the oxidized state of arsenite oxidase.