Theoretical studies of [FeFe]-hydrogenase: Structure and infrared spectra of synthetic models

Silviu Zilberman; Edward I. Stiefel; Morrel H. Cohen; Roberto Car

doi:10.1021/jp056551z

Theoretical studies of [FeFe]-hydrogenase: Structure and infrared spectra of synthetic models

Silviu Zilberman, Edward I. Stiefel, Morrel H. Cohen, Roberto Car

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25 Scopus citations

Abstract

First-principles density functional theory calculations of synthetic models of [FeFe]-hydrogenase are used to show that the theoretical methods reproduce observed structures and infrared spectra to high accuracy. The accuracy is demonstrated for synthetic Fe(I)Fe(I) models ([(μ-PDT)Fe₂(CO) ₆] and [(CN)(CO)₂(μ-PDT)Fe₂-(CO) ₂(CN)]^2-), for which we show that their infrared spectra are sensitive to the geometric arrangement of their CO/CN ligands and can be used in conjunction with quantum-mechanical total energies to predict the correct ligand geometry. We then analyze and predict the structure of mixed-valence Fe(II)Fe(I) models ([(μ-MeSCH₂C(Me)(CH ₂S)₂)Fe₂(CO)₄(CN)₂[ ^x-). These capabilities promise to distinguish among the various structural isomers of the enzyme's active site which are consistent with the limited accuracy of the X-ray observations.

Original language	English (US)
Pages (from-to)	7049-7057
Number of pages	9
Journal	Journal of Physical Chemistry B
Volume	110
Issue number	13
DOIs	https://doi.org/10.1021/jp056551z
State	Published - May 6 2006

All Science Journal Classification (ASJC) codes

Materials Chemistry
Surfaces, Coatings and Films
Physical and Theoretical Chemistry

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@article{d3eb3cde0a85420ca3d718bbc1b113dc,

title = "Theoretical studies of [FeFe]-hydrogenase: Structure and infrared spectra of synthetic models",

abstract = "First-principles density functional theory calculations of synthetic models of [FeFe]-hydrogenase are used to show that the theoretical methods reproduce observed structures and infrared spectra to high accuracy. The accuracy is demonstrated for synthetic Fe(I)Fe(I) models ([(μ-PDT)Fe2(CO) 6] and [(CN)(CO)2(μ-PDT)Fe2-(CO) 2(CN)]2-), for which we show that their infrared spectra are sensitive to the geometric arrangement of their CO/CN ligands and can be used in conjunction with quantum-mechanical total energies to predict the correct ligand geometry. We then analyze and predict the structure of mixed-valence Fe(II)Fe(I) models ([(μ-MeSCH2C(Me)(CH 2S)2)Fe2(CO)4(CN)2[ x-). These capabilities promise to distinguish among the various structural isomers of the enzyme's active site which are consistent with the limited accuracy of the X-ray observations.",

author = "Silviu Zilberman and Stiefel, {Edward I.} and Cohen, {Morrel H.} and Roberto Car",

year = "2006",

month = may,

day = "6",

doi = "10.1021/jp056551z",

language = "English (US)",

volume = "110",

pages = "7049--7057",

journal = "Journal of Physical Chemistry B",

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publisher = "American Chemical Society",

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TY - JOUR

T1 - Theoretical studies of [FeFe]-hydrogenase

T2 - Structure and infrared spectra of synthetic models

AU - Zilberman, Silviu

AU - Stiefel, Edward I.

AU - Cohen, Morrel H.

AU - Car, Roberto

PY - 2006/5/6

Y1 - 2006/5/6

N2 - First-principles density functional theory calculations of synthetic models of [FeFe]-hydrogenase are used to show that the theoretical methods reproduce observed structures and infrared spectra to high accuracy. The accuracy is demonstrated for synthetic Fe(I)Fe(I) models ([(μ-PDT)Fe2(CO) 6] and [(CN)(CO)2(μ-PDT)Fe2-(CO) 2(CN)]2-), for which we show that their infrared spectra are sensitive to the geometric arrangement of their CO/CN ligands and can be used in conjunction with quantum-mechanical total energies to predict the correct ligand geometry. We then analyze and predict the structure of mixed-valence Fe(II)Fe(I) models ([(μ-MeSCH2C(Me)(CH 2S)2)Fe2(CO)4(CN)2[ x-). These capabilities promise to distinguish among the various structural isomers of the enzyme's active site which are consistent with the limited accuracy of the X-ray observations.

AB - First-principles density functional theory calculations of synthetic models of [FeFe]-hydrogenase are used to show that the theoretical methods reproduce observed structures and infrared spectra to high accuracy. The accuracy is demonstrated for synthetic Fe(I)Fe(I) models ([(μ-PDT)Fe2(CO) 6] and [(CN)(CO)2(μ-PDT)Fe2-(CO) 2(CN)]2-), for which we show that their infrared spectra are sensitive to the geometric arrangement of their CO/CN ligands and can be used in conjunction with quantum-mechanical total energies to predict the correct ligand geometry. We then analyze and predict the structure of mixed-valence Fe(II)Fe(I) models ([(μ-MeSCH2C(Me)(CH 2S)2)Fe2(CO)4(CN)2[ x-). These capabilities promise to distinguish among the various structural isomers of the enzyme's active site which are consistent with the limited accuracy of the X-ray observations.

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U2 - 10.1021/jp056551z

DO - 10.1021/jp056551z

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AN - SCOPUS:33646360588

SN - 1520-6106

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JO - Journal of Physical Chemistry B

JF - Journal of Physical Chemistry B

IS - 13

ER -

Theoretical studies of [FeFe]-hydrogenase: Structure and infrared spectra of synthetic models

Abstract

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