Terminal hydride in [FeFe]-hydrogenase model has lower potential for H 2 production than the isomeric bridging hydride

Bryan E. Barton; Thomas B. Rauchfuss

doi:10.1021/ic800030y

Terminal hydride in [FeFe]-hydrogenase model has lower potential for H ₂ production than the isomeric bridging hydride

Bryan E. Barton
, Thomas B. Rauchfuss

Chemistry

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

Abstract

Protonation of the symmetrical tetraphosphine complexes Fe ₂(S₂C_nH_2n)(CO)₂(dppv) ₂ afforded the corresponding terminal hydrides, establishing that even symmetrical diiron(I) dithiolates undergo protonation at terminal sites. The terminal hydride [HFe₂(S₂C₃H ₆)(CO)₂(dppv)₂]⁺ was found to catalyze proton reduction at potentials 200 mV milder than the isomeric bridging hydride, thereby establishing a thermodynamic advantage for catalysis operating via terminal hydride. The azadithiolate protonates to afford, [Fe ₂[(SCH₂)₂NH₂](CO) ₂(dppv)₂]⁺, [HFe₂[(SCH ₂)₂NH](CO)₂-(dppv)₂]⁺, and [HFe₂[(SCH₂)₂NH₂](CO) ₂(dppv)₂]²⁺, depending on conditions.

Original language	English (US)
Pages (from-to)	2261-2263
Number of pages	3
Journal	Inorganic Chemistry
Volume	47
Issue number	7
DOIs	https://doi.org/10.1021/ic800030y
State	Published - Apr 7 2008

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/ic800030y

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Cite this

@article{fea65e2d4fb3458c82761755a448ebf2,

title = "Terminal hydride in [FeFe]-hydrogenase model has lower potential for H 2 production than the isomeric bridging hydride",

abstract = "Protonation of the symmetrical tetraphosphine complexes Fe 2(S2CnH2n)(CO)2(dppv) 2 afforded the corresponding terminal hydrides, establishing that even symmetrical diiron(I) dithiolates undergo protonation at terminal sites. The terminal hydride [HFe2(S2C3H 6)(CO)2(dppv)2]+ was found to catalyze proton reduction at potentials 200 mV milder than the isomeric bridging hydride, thereby establishing a thermodynamic advantage for catalysis operating via terminal hydride. The azadithiolate protonates to afford, [Fe 2[(SCH2)2NH2](CO) 2(dppv)2]+, [HFe2[(SCH 2)2NH](CO)2-(dppv)2]+, and [HFe2[(SCH2)2NH2](CO) 2(dppv)2]2+, depending on conditions.",

author = "Barton, \{Bryan E.\} and Rauchfuss, \{Thomas B.\}",

year = "2008",

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doi = "10.1021/ic800030y",

language = "English (US)",

volume = "47",

pages = "2261--2263",

journal = "Inorganic Chemistry",

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TY - JOUR

T1 - Terminal hydride in [FeFe]-hydrogenase model has lower potential for H 2 production than the isomeric bridging hydride

AU - Barton, Bryan E.

AU - Rauchfuss, Thomas B.

PY - 2008/4/7

Y1 - 2008/4/7

N2 - Protonation of the symmetrical tetraphosphine complexes Fe 2(S2CnH2n)(CO)2(dppv) 2 afforded the corresponding terminal hydrides, establishing that even symmetrical diiron(I) dithiolates undergo protonation at terminal sites. The terminal hydride [HFe2(S2C3H 6)(CO)2(dppv)2]+ was found to catalyze proton reduction at potentials 200 mV milder than the isomeric bridging hydride, thereby establishing a thermodynamic advantage for catalysis operating via terminal hydride. The azadithiolate protonates to afford, [Fe 2[(SCH2)2NH2](CO) 2(dppv)2]+, [HFe2[(SCH 2)2NH](CO)2-(dppv)2]+, and [HFe2[(SCH2)2NH2](CO) 2(dppv)2]2+, depending on conditions.

AB - Protonation of the symmetrical tetraphosphine complexes Fe 2(S2CnH2n)(CO)2(dppv) 2 afforded the corresponding terminal hydrides, establishing that even symmetrical diiron(I) dithiolates undergo protonation at terminal sites. The terminal hydride [HFe2(S2C3H 6)(CO)2(dppv)2]+ was found to catalyze proton reduction at potentials 200 mV milder than the isomeric bridging hydride, thereby establishing a thermodynamic advantage for catalysis operating via terminal hydride. The azadithiolate protonates to afford, [Fe 2[(SCH2)2NH2](CO) 2(dppv)2]+, [HFe2[(SCH 2)2NH](CO)2-(dppv)2]+, and [HFe2[(SCH2)2NH2](CO) 2(dppv)2]2+, depending on conditions.

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

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