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

Online availability

10.1021/ja055475a

Library availability

Discover UIUC Full Text

Cite this

@article{0763f6244618499e89d1559e3844509a,

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.",

author = "{Van Der Vlugt}, {Jarl Ivar} and Rauchfuss, {Thomas B.} and Whaley, {C. Matthew} and Wilson, {Scott R.}",

year = "2005",

month = nov,

day = "23",

doi = "10.1021/ja055475a",

language = "English (US)",

volume = "127",

pages = "16012--16013",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "46",

}

TY - JOUR

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.

UR - http://www.scopus.com/inward/record.url?scp=28044448515&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=28044448515&partnerID=8YFLogxK

U2 - 10.1021/ja055475a

DO - 10.1021/ja055475a

M3 - Article

C2 - 16287273

AN - SCOPUS:28044448515

SN - 0002-7863

VL - 127

SP - 16012

EP - 16013

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 46

ER -

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

Abstract

ASJC Scopus subject areas

Online availability

Library availability

Related links

Fingerprint

Cite this