Dihydrogen activation by a diruthenium analogue of the Fe-only hydrogenase active site

被引：59

作者：

Justice, AK ^{[1
]}

Linck, RC ^{[1
]}

Rauchfuss, TB ^{[1
]}

Wilson, SR ^{[1
]}

机构：

[1] Univ Illinois, Dept Chem, Urbana, IL 61801 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2004年 / 126卷 / 41期

关键词：

D O I：

10.1021/ja0455594

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The photochemical reaction of Ru2(S2C3H6)(CO)4(PCy3)2 (1) and H2 gives the dihydride Ru2(S2C3H6)(μ-H)(H)(CO)3(PCy3)2 (2). NMR and crystallographic studies reveal mutually trans basal phosphine ligands and both bridging and terminal hydrides. Ru2(S2C2H4)(CO)4(PCy3)2 behaves similarly. Other HX substrates undergo photoaddition to 1, affording Ru2(S2C3H6)(μ-H)(X)(CO)3(PCy3)2 for X = OTs (3a), Cl (3b), and SPh (3c). Treatment of Ru2(S2C3H6)(μ-H)(H)(CO)3(PCy3)2 with [H(OEt2)]BArF4 (ArF = B(C6H3-3,5-(CF3)2) in CD2Cl2 gives [Ru2(S2C3H6)(μ-H)(CO)3(PCy3)2(H2)]+ (4), which catalyzes H2-D2 exchange. The reaction of 2 with [D(OEt2)]BArF4 gave [Ru2(S2C3H6)(μ-H)(CO)3(PCy3)2(HD)]+ (JH-D = 31 Hz). These studies provide the first models for the Fe-only hydrogenases that bear dihydrogen and terminal hydrido ligands. Copyright © 2004 American Chemical Society.

引用

页码：13214 / 13215

页数：2

共 19 条

[11] Binuclear ruthenium complexes containing bridging dithiolate and dppm ligands:: X-ray structures of [Ru2(CO)4(μ-SCH2CH2CH2S)(μ-dppm)] and [Ru2(CO)4{(μ-SC6H3(CH3)S}(μ-dppm)] [J].