Heterobimetallic [NiFe] Complexes Containing Mixed CO/CN- Ligands: Analogs of the Active Site of the [NiFe] Hydrogenases.
Inorg Chem
; 57(5): 2558-2569, 2018 Mar 05.
Article
em En
| MEDLINE
| ID: mdl-29465237
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( N2 S2)Fe(CO)2(CN)2], [Ni( S4)Fe(CO)2(CN)2], and [Ni( N2 S3)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( N2 S3)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 and -1.67 V vs Fc+/Fc and [Ni( N2 S3)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( N2 S3)Fe(CO)2(CN)2]+. The singly occupied molecular orbital (SOMO) in [Ni( N2 S3)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( N2 S3)Fe(CO)2(CN)2] and its [Ni( N2 S3)] precursor, together with calculations on the oxidized [Ni( N2 S3)Fe(CO)2(CN)2]+ and [Ni( N2 S3)]+ 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.
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Base de dados:
MEDLINE
Assunto principal:
Monóxido de Carbono
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Cianetos
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Complexos de Coordenação
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Hidrogenase
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Ferro
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Níquel
Idioma:
En
Ano de publicação:
2018
Tipo de documento:
Article