Characterization of a diferrous terminal hydride mechanistically relevant to the Fe-only hydrogenases

Jarl Ivar Van Der Vlugt; Thomas B. Rauchfuss; C. Matthew Whaley; Scott R. Wilson

doi:10.1021/ja055475a

Characterization of a diferrous terminal hydride mechanistically relevant to the Fe-only hydrogenases

Jarl Ivar Van Der Vlugt, Thomas B. Rauchfuss, C. Matthew Whaley, Scott R. Wilson

Chemistry

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

Abstract

Reduction of diferrous dithiolato complexes with hydride donor reagents affords the first example of the previously elusive terminal diferrous hydride, [Fe₂(edt)(μ-CO)(H)(CO)(PMe₃)₄]PF₆ (edt = S₂C₂H₄). Crystallographic characterization shows that this model contains an asymmetrical semi-bridging CO trans to a terminal hydrido, as indicated in the H_red state in the D. desulfuricans enzyme. The model reacts with protons to yield H₂ and rearranges via an intramolecular process to the isomeric μ-hydrido isomer, which is unreactive toward protons.

Original language	English (US)
Pages (from-to)	16012-16013
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	127
Issue number	46
DOIs	https://doi.org/10.1021/ja055475a
State	Published - Nov 23 2005

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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title = "Characterization of a diferrous terminal hydride mechanistically relevant to the Fe-only hydrogenases",

abstract = "Reduction of diferrous dithiolato complexes with hydride donor reagents affords the first example of the previously elusive terminal diferrous hydride, [Fe2(edt)(μ-CO)(H)(CO)(PMe3)4]PF6 (edt = S2C2H4). Crystallographic characterization shows that this model contains an asymmetrical semi-bridging CO trans to a terminal hydrido, as indicated in the Hred state in the D. desulfuricans enzyme. The model reacts with protons to yield H2 and rearranges via an intramolecular process to the isomeric μ-hydrido isomer, which is unreactive toward protons.",

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T1 - Characterization of a diferrous terminal hydride mechanistically relevant to the Fe-only hydrogenases

AU - Van Der Vlugt, Jarl Ivar

AU - Rauchfuss, Thomas B.

AU - Whaley, C. Matthew

AU - Wilson, Scott R.

PY - 2005/11/23

Y1 - 2005/11/23

N2 - Reduction of diferrous dithiolato complexes with hydride donor reagents affords the first example of the previously elusive terminal diferrous hydride, [Fe2(edt)(μ-CO)(H)(CO)(PMe3)4]PF6 (edt = S2C2H4). Crystallographic characterization shows that this model contains an asymmetrical semi-bridging CO trans to a terminal hydrido, as indicated in the Hred state in the D. desulfuricans enzyme. The model reacts with protons to yield H2 and rearranges via an intramolecular process to the isomeric μ-hydrido isomer, which is unreactive toward protons.

AB - Reduction of diferrous dithiolato complexes with hydride donor reagents affords the first example of the previously elusive terminal diferrous hydride, [Fe2(edt)(μ-CO)(H)(CO)(PMe3)4]PF6 (edt = S2C2H4). Crystallographic characterization shows that this model contains an asymmetrical semi-bridging CO trans to a terminal hydrido, as indicated in the Hred state in the D. desulfuricans enzyme. The model reacts with protons to yield H2 and rearranges via an intramolecular process to the isomeric μ-hydrido isomer, which is unreactive toward protons.

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Characterization of a diferrous terminal hydride mechanistically relevant to the Fe-only hydrogenases

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