Synthesis, gas-phase photoelectron spectroscopic, and theoretical studies of stannylated dinuclear iron dithiolates

Richard S. Glass; Nadine E. Gruhn; Edward Lorance; Maya S. Singh; Nhu Y.T. Stessman; Uzma I. Zakai

doi:10.1021/ic050526q

Synthesis, gas-phase photoelectron spectroscopic, and theoretical studies of stannylated dinuclear iron dithiolates

Richard S. Glass, Nadine E. Gruhn, Edward Lorance, Maya S. Singh, Nhu Y.T. Stessman, Uzma I. Zakai

Chemistry and Biochemistry

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

19 Scopus citations

Abstract

Stannylated dinuclear iron dithiolates (μ-SSnMe₂CH ₂S)[Fe(CO)₃]₂, (μ-SCH₂SnMe ₂CH₂S) [Fe(CO)₃]₂, and (μ-SCH₂-SnMe₃)₂[Fe(CO)₃] ₂, which are structurally similar to the active site of iron-only hydrogenase, were synthesized and studied by gas-phase photoelectron spectroscopy. The orbital origins of ionizations were assigned by comparison of He I and He II photoelectron spectra and with the aid of hybrid density functional electronic structure calculations. Stannylation lowers the ionization energy of sulfur lone pair orbitals in these systems owing to a geometry-dependent interaction. The Fe-Fe σ bond, which is the HOMO in all these systems, is also substantially destabilized by stannylation due to a previously unrecognized geometry-dependent interaction between axial sulfur lone pair orbitals and the Fe-Fe σ bond. Since cleaving the Fe-Fe σ bond is a key step in the mechanism of action of iron-only hydrogenase, these newly recognized geometry-dependent interactions may be utilized in designing biologically inspired hydrogenase catalysts.

Original language	English (US)
Pages (from-to)	5728-5737
Number of pages	10
Journal	Inorganic Chemistry
Volume	44
Issue number	16
DOIs	https://doi.org/10.1021/ic050526q
State	Published - Aug 8 2005

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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title = "Synthesis, gas-phase photoelectron spectroscopic, and theoretical studies of stannylated dinuclear iron dithiolates",

abstract = "Stannylated dinuclear iron dithiolates (μ-SSnMe2CH 2S)[Fe(CO)3]2, (μ-SCH2SnMe 2CH2S) [Fe(CO)3]2, and (μ-SCH2-SnMe3)2[Fe(CO)3] 2, which are structurally similar to the active site of iron-only hydrogenase, were synthesized and studied by gas-phase photoelectron spectroscopy. The orbital origins of ionizations were assigned by comparison of He I and He II photoelectron spectra and with the aid of hybrid density functional electronic structure calculations. Stannylation lowers the ionization energy of sulfur lone pair orbitals in these systems owing to a geometry-dependent interaction. The Fe-Fe σ bond, which is the HOMO in all these systems, is also substantially destabilized by stannylation due to a previously unrecognized geometry-dependent interaction between axial sulfur lone pair orbitals and the Fe-Fe σ bond. Since cleaving the Fe-Fe σ bond is a key step in the mechanism of action of iron-only hydrogenase, these newly recognized geometry-dependent interactions may be utilized in designing biologically inspired hydrogenase catalysts.",

author = "Glass, {Richard S.} and Gruhn, {Nadine E.} and Edward Lorance and Singh, {Maya S.} and Stessman, {Nhu Y.T.} and Zakai, {Uzma I.}",

year = "2005",

month = aug,

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doi = "10.1021/ic050526q",

language = "English (US)",

volume = "44",

pages = "5728--5737",

journal = "Inorganic Chemistry",

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T1 - Synthesis, gas-phase photoelectron spectroscopic, and theoretical studies of stannylated dinuclear iron dithiolates

AU - Glass, Richard S.

AU - Gruhn, Nadine E.

AU - Lorance, Edward

AU - Singh, Maya S.

AU - Stessman, Nhu Y.T.

AU - Zakai, Uzma I.

PY - 2005/8/8

Y1 - 2005/8/8

N2 - Stannylated dinuclear iron dithiolates (μ-SSnMe2CH 2S)[Fe(CO)3]2, (μ-SCH2SnMe 2CH2S) [Fe(CO)3]2, and (μ-SCH2-SnMe3)2[Fe(CO)3] 2, which are structurally similar to the active site of iron-only hydrogenase, were synthesized and studied by gas-phase photoelectron spectroscopy. The orbital origins of ionizations were assigned by comparison of He I and He II photoelectron spectra and with the aid of hybrid density functional electronic structure calculations. Stannylation lowers the ionization energy of sulfur lone pair orbitals in these systems owing to a geometry-dependent interaction. The Fe-Fe σ bond, which is the HOMO in all these systems, is also substantially destabilized by stannylation due to a previously unrecognized geometry-dependent interaction between axial sulfur lone pair orbitals and the Fe-Fe σ bond. Since cleaving the Fe-Fe σ bond is a key step in the mechanism of action of iron-only hydrogenase, these newly recognized geometry-dependent interactions may be utilized in designing biologically inspired hydrogenase catalysts.

AB - Stannylated dinuclear iron dithiolates (μ-SSnMe2CH 2S)[Fe(CO)3]2, (μ-SCH2SnMe 2CH2S) [Fe(CO)3]2, and (μ-SCH2-SnMe3)2[Fe(CO)3] 2, which are structurally similar to the active site of iron-only hydrogenase, were synthesized and studied by gas-phase photoelectron spectroscopy. The orbital origins of ionizations were assigned by comparison of He I and He II photoelectron spectra and with the aid of hybrid density functional electronic structure calculations. Stannylation lowers the ionization energy of sulfur lone pair orbitals in these systems owing to a geometry-dependent interaction. The Fe-Fe σ bond, which is the HOMO in all these systems, is also substantially destabilized by stannylation due to a previously unrecognized geometry-dependent interaction between axial sulfur lone pair orbitals and the Fe-Fe σ bond. Since cleaving the Fe-Fe σ bond is a key step in the mechanism of action of iron-only hydrogenase, these newly recognized geometry-dependent interactions may be utilized in designing biologically inspired hydrogenase catalysts.

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Synthesis, gas-phase photoelectron spectroscopic, and theoretical studies of stannylated dinuclear iron dithiolates

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