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

Aaron K. Justice; Rachel C. Linck; Thomas B. Rauchfuss; Scott R. Wilson

doi:10.1021/ja0455594

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

Aaron K. Justice
, Rachel C. Linck
, Thomas B. Rauchfuss
, Scott R. Wilson

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

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)]BAr^F₄ (Ar^F = 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)]BAr^F₄ gave [Ru₂(S₂C₃H₆)(μ-H)(CO)₃(PCy₃)₂(HD)]⁺ (J_H-D = 31 Hz). These studies provide the first models for the Fe-only hydrogenases that bear dihydrogen and terminal hydrido ligands.

Original language	English (US)
Pages (from-to)	13214-13215
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	126
Issue number	41
DOIs	https://doi.org/10.1021/ja0455594
State	Published - Oct 20 2004

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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10.1021/ja0455594

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title = "Dihydrogen activation by a diruthenium analogue of the Fe-only hydrogenase active site",

abstract = "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.",

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AU - Wilson, Scott R.

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N2 - 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.

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

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