Low-Potential Cyclometalated Osmium(II) Mediators of Glucose Oxidase
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- 作者：Alexander D. Ryabov ; Valentin S. Soukharev ; Larissa Alexandrova ; Ronan Le Lagadec ; and Michel Pfeffer
- 刊名：Inorganic Chemistry
- 出版年：2003
- 出版时间：October 20, 2003
- 年：2003
- 卷：42
- 期：21
- 页码：6598 - 6600
- 全文大小：80K
- 年卷期：v.42,no.21(October 20, 2003)
- ISSN：1520-510X
文摘
The osma(II)cycles [Os(phpy)(LL)2]PF6 (LL = 1,10-phen (3a) and4,4'-Me2-2,2'-bpy (3b)) are made from [(
6-C6H6)Os(
-Cl)Cl]2 (1)either via transmetalation using the [Hg(phpy)2] organomercurialin MeOH or via the sp2-C-H bond cleavage of 2-phenylpyridine(phpyH) in MeCN to afford [(6-C6H6)Os(phpy)Cl] or [(6-C6H6)Os(phpy)(MeCN)]PF6, respectively. The latter two react cleanly withLL to give 3a and 3b, the MII/III redox potentials of which equal 30and -100 mV (vs Ag/AgCl), respectively. The electrochemicallymade OsIII species oxidize rapidly reduced glucose oxidase. Thesecond-order rate constant equals 1.1 × 107 M-1 s-1 for 3a at 25
C, pH 7.
6-C6H6)Os(-Cl)Cl]2 (1)either via transmetalation using the [Hg(phpy)2] organomercurialin MeOH or via the sp2-C-H bond cleavage of 2-phenylpyridine(phpyH) in MeCN to afford [(6-C6H6)Os(phpy)Cl] or [(6-C6H6)Os(phpy)(MeCN)]PF6, respectively. The latter two react cleanly withLL to give 3a and 3b, the MII/III redox potentials of which equal 30and -100 mV (vs Ag/AgCl), respectively. The electrochemicallymade OsIII species oxidize rapidly reduced glucose oxidase. Thesecond-order rate constant equals 1.1 × 107 M-1 s-1 for 3a at 25C, pH 7.