Electronic and Magnetic Properties of Nickel-Substituted Rubredoxin: A Variable-Temperature Magnetic Circular Dichroism Study

Andrzej T. Kowal; Jean LeGall; Michael K. Johnson; Isabel C. Zambrano; Isabel Moura; José J. G. Moura

doi:10.1021/ic00280a015

Electronic and Magnetic Properties of Nickel-Substituted Rubredoxin: A Variable-Temperature Magnetic Circular Dichroism Study

Andrzej T. Kowal, Jean LeGall, Michael K. Johnson, Isabel C. Zambrano, Isabel Moura, José J. G. Moura

Universidade NOVA de Lisboa

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

80 Citations (Scopus)

Abstract

Ni(II)-substituted rubredoxins from Desulfovibrio gigas, Desulfovibrio vulgaris, and Clostridium pasteurianum have been prepared and characterized by room-temperature UV-visible absorption and low-temperature MCD spectroscopy. The results are compared with those obtained for the crystallographically defined analogue complex (Ph₄P)₂Ni(SPh)₄. The Ni(II) sites in both the biological and inorganic compounds are found to be high spin, with very similar electronic and magnetic properties. The results are interpreted in terms of tetragonally distorted tetrahedral thiolate coordination for Ni(II), resulting in a ³A₂ ground state, under D_2d symmetry, that is subject to large axial zero-field splitting. Studies of the temperature dependence of the solution MCD spectra facilitate quantitative assessment of the axial zero-field splitting parameters; D = 55 cm^-1 for Ni(II)-substituted Rd and D = 44 cm^-1 for Ni(SPh)₄^2-. The properties of Ni(II) sites in hydrogenases are discussed in light of these results.

Original language	English
Pages (from-to)	1162-1166
Number of pages	5
Journal	Inorganic Chemistry
Volume	27
Issue number	7
DOIs	https://doi.org/10.1021/ic00280a015
Publication status	Published - 1 Apr 1988

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@article{81da3874033844219d770b3d70ab455a,

title = "Electronic and Magnetic Properties of Nickel-Substituted Rubredoxin: A Variable-Temperature Magnetic Circular Dichroism Study",

abstract = "Ni(II)-substituted rubredoxins from Desulfovibrio gigas, Desulfovibrio vulgaris, and Clostridium pasteurianum have been prepared and characterized by room-temperature UV-visible absorption and low-temperature MCD spectroscopy. The results are compared with those obtained for the crystallographically defined analogue complex (Ph4P)2Ni(SPh)4. The Ni(II) sites in both the biological and inorganic compounds are found to be high spin, with very similar electronic and magnetic properties. The results are interpreted in terms of tetragonally distorted tetrahedral thiolate coordination for Ni(II), resulting in a 3A2 ground state, under D2d symmetry, that is subject to large axial zero-field splitting. Studies of the temperature dependence of the solution MCD spectra facilitate quantitative assessment of the axial zero-field splitting parameters; D = 55 cm-1 for Ni(II)-substituted Rd and D = 44 cm-1 for Ni(SPh)42-. The properties of Ni(II) sites in hydrogenases are discussed in light of these results.",

author = "Kowal, {Andrzej T.} and Jean LeGall and Johnson, {Michael K.} and Zambrano, {Isabel C.} and Isabel Moura and Moura, {Jos{\'e} J. G.}",

year = "1988",

month = apr,

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doi = "10.1021/ic00280a015",

language = "English",

volume = "27",

pages = "1162--1166",

journal = "Inorganic Chemistry",

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publisher = "ACS - American Chemical Society",

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T1 - Electronic and Magnetic Properties of Nickel-Substituted Rubredoxin: A Variable-Temperature Magnetic Circular Dichroism Study

AU - Kowal, Andrzej T.

AU - LeGall, Jean

AU - Johnson, Michael K.

AU - Zambrano, Isabel C.

AU - Moura, Isabel

AU - Moura, José J. G.

PY - 1988/4/1

Y1 - 1988/4/1

N2 - Ni(II)-substituted rubredoxins from Desulfovibrio gigas, Desulfovibrio vulgaris, and Clostridium pasteurianum have been prepared and characterized by room-temperature UV-visible absorption and low-temperature MCD spectroscopy. The results are compared with those obtained for the crystallographically defined analogue complex (Ph4P)2Ni(SPh)4. The Ni(II) sites in both the biological and inorganic compounds are found to be high spin, with very similar electronic and magnetic properties. The results are interpreted in terms of tetragonally distorted tetrahedral thiolate coordination for Ni(II), resulting in a 3A2 ground state, under D2d symmetry, that is subject to large axial zero-field splitting. Studies of the temperature dependence of the solution MCD spectra facilitate quantitative assessment of the axial zero-field splitting parameters; D = 55 cm-1 for Ni(II)-substituted Rd and D = 44 cm-1 for Ni(SPh)42-. The properties of Ni(II) sites in hydrogenases are discussed in light of these results.

AB - Ni(II)-substituted rubredoxins from Desulfovibrio gigas, Desulfovibrio vulgaris, and Clostridium pasteurianum have been prepared and characterized by room-temperature UV-visible absorption and low-temperature MCD spectroscopy. The results are compared with those obtained for the crystallographically defined analogue complex (Ph4P)2Ni(SPh)4. The Ni(II) sites in both the biological and inorganic compounds are found to be high spin, with very similar electronic and magnetic properties. The results are interpreted in terms of tetragonally distorted tetrahedral thiolate coordination for Ni(II), resulting in a 3A2 ground state, under D2d symmetry, that is subject to large axial zero-field splitting. Studies of the temperature dependence of the solution MCD spectra facilitate quantitative assessment of the axial zero-field splitting parameters; D = 55 cm-1 for Ni(II)-substituted Rd and D = 44 cm-1 for Ni(SPh)42-. The properties of Ni(II) sites in hydrogenases are discussed in light of these results.

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U2 - 10.1021/ic00280a015

DO - 10.1021/ic00280a015

M3 - Article

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SN - 0020-1669

VL - 27

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EP - 1166

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 7

ER -

Electronic and Magnetic Properties of Nickel-Substituted Rubredoxin: A Variable-Temperature Magnetic Circular Dichroism Study

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