Carlo U. Perotto
Heterobimetallic [NiFe] complexes containing mixedCO/CN− ligands: analogs of the active site of the [NiFe]hydrogenases
Perotto, Carlo U.; Sodipo, Charlene L.; Jones, Graham J.; Tidey, Jeremiah P.; Blake, Alexander J.; Lewis, William; Davies, E. Stephen; McMaster, Jonathan; Schröder, Martin
Authors
Charlene L. Sodipo
Graham J. Jones
Jeremiah P. Tidey
Alexander J. Blake
William Lewis
STEPHEN DAVIES e.s.davies@nottingham.ac.uk
Research Officer
JONATHAN MCMASTER Jonathan.McMaster@nottingham.ac.uk
Professor of Chemistry
Martin Schröder
Abstract
The development of synthetic analogs of the active sites of [NiFe] hydrogenases remains challenging and, in spite of the number of complexes featuring a [NiFe] center, those featuring CO and CN− ligands at the Fe center are under-represented. We report herein the synthesis of three bimetallic [NiFe] complexes [Ni(N2S2)Fe(CO)2(CN)2], [Ni(S4)Fe(CO)2(CN)2] and [Ni(N2S3)Fe(CO)2(CN)2] that each contain a Ni center that bridges through two thiolato S donors to a {Fe(CO)2(CN)2} unit. X-ray crystallographic studies on [Ni(N2S3)Fe(CO)2(CN)2], supported by DFT calculations, are consistent with a solid state structure containing distinct molecules in the singlet (S = 0) and triplet (S = 1) states. Each cluster exhibits irreversible reduction processes between −1.45 to −1.67 V vs Fc+/Fc and [Ni(N2S3)Fe(CO)2(CN)2] possesses a reversible oxidation process at 0.17 V vs Fc+/Fc. Spectroelectrochemical infrared (IR) and electron paramagnetic resonance (EPR) studies, supported by density functional theory (DFT) calculations, are consistent with a NiIIIFeII formulation for [Ni(N2S3)Fe(CO)2(CN)2]+. The SOMO in [Ni(N2S3)Fe(CO)2(CN)2]+ is based on Ni 3dz² and 3p S with the S contributions deriving principally from the apical S-donor. The nature of the SOMO corresponds to that proposed for the Ni-C state of the [NiFe] hydrogenases for which a NiIIIFeII formulation has also been proposed. A comparison of the experimental structures, and the electrochemical and spectroscopic properties of [Ni(N2S3)Fe(CO)2(CN)2] and its [Ni(N2S3)] precursor, together with calculations on the oxidized [Ni(N2S3)Fe(CO)2(CN)2]+ and [Ni(N2S3)]+ forms suggests that the binding of the {Fe(CO)(CN)2} unit to the {Ni(CysS)4} center at the active site of the [NiFe] hydrogenases suppresses thiolate-based oxidative chemistry involving the bridging thiolate S donors. This is in addition to the role of the Fe center in modulating the redox potential and geometry, and supporting a bridging hydride species between the Ni and Fe centers in the Ni-C state..
Citation
Perotto, C. U., Sodipo, C. L., Jones, G. J., Tidey, J. P., Blake, A. J., Lewis, W., Davies, E. S., McMaster, J., & Schröder, M. (in press). Heterobimetallic [NiFe] complexes containing mixedCO/CN− ligands: analogs of the active site of the [NiFe]hydrogenases. Inorganic Chemistry, 57(5), https://doi.org/10.1021/acs.inorgchem.7b02905
Journal Article Type | Article |
---|---|
Acceptance Date | Oct 12, 2017 |
Online Publication Date | Feb 21, 2018 |
Deposit Date | Feb 26, 2018 |
Publicly Available Date | Feb 22, 2019 |
Journal | Inorganic Chemistry |
Print ISSN | 0020-1669 |
Electronic ISSN | 1520-510X |
Publisher | American Chemical Society |
Peer Reviewed | Peer Reviewed |
Volume | 57 |
Issue | 5 |
DOI | https://doi.org/10.1021/acs.inorgchem.7b02905 |
Public URL | https://nottingham-repository.worktribe.com/output/913229 |
Publisher URL | https://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.7b02905 |
Additional Information | This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.7b02905 |
Contract Date | Feb 26, 2018 |
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