Bioinspired Nickel Complexes Supported by an Iron Metalloligand

Jacob R Prat; Carlo Alberto Gaggioli; Ryan C. Cammarota; Eckhard Bill; Laura Gagliardi; Connie C. Lu

doi:10.1021/acs.inorgchem.0c02041

Bioinspired Nickel Complexes Supported by an Iron Metalloligand

Jacob R Prat, Carlo Alberto Gaggioli, Ryan C. Cammarota, Eckhard Bill, Laura Gagliardi, Connie C. Lu

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

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Abstract

Nature utilizes multimetallic sites in metalloenzymes to enable multielectron chemical transformations at ambient conditions and low overpotentials. One such example of multimetallic cooperativity can be found in the C-cluster of Ni-carbon monoxide dehydrogenase (CODH), which interconverts CO and CO2. Toward a potential functional model of the C-cluster, a family of Ni-Fe bimetallic complexes was synthesized that contain direct metal-metal bonding interactions. The complexes were characterized by X-ray crystallography, various spectroscopies (NMR, EPR, UV-vis, Mössbauer), and theoretical calculations. The Ni-Fe bimetallic system has a reversible Fe(III)/Fe(II) redox couple at -2.10 V (vs Fc+/Fc). The Fe-based "redox switch"can turn on CO2 reactivity at the Ni(0) center by leveraging the Ni→Fe dative interaction to attenuate the Ni(0) electron density. The reduced Ni(0)Fe(II) species mediated the formal two-electron reduction of CO2 to CO, providing a Ni-CO adduct and CO32- as products. During the reaction, an intermediate was observed that is proposed to be a Ni-CO2 species.

Original language	English (US)
Pages (from-to)	14251-14262
Number of pages	12
Journal	Inorganic chemistry
Volume	59
Issue number	19
DOIs	https://doi.org/10.1021/acs.inorgchem.0c02041
State	Published - Oct 5 2020

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© 2020 American Chemical Society.

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abstract = "Nature utilizes multimetallic sites in metalloenzymes to enable multielectron chemical transformations at ambient conditions and low overpotentials. One such example of multimetallic cooperativity can be found in the C-cluster of Ni-carbon monoxide dehydrogenase (CODH), which interconverts CO and CO2. Toward a potential functional model of the C-cluster, a family of Ni-Fe bimetallic complexes was synthesized that contain direct metal-metal bonding interactions. The complexes were characterized by X-ray crystallography, various spectroscopies (NMR, EPR, UV-vis, M{\"o}ssbauer), and theoretical calculations. The Ni-Fe bimetallic system has a reversible Fe(III)/Fe(II) redox couple at -2.10 V (vs Fc+/Fc). The Fe-based {"}redox switch{"}can turn on CO2 reactivity at the Ni(0) center by leveraging the Ni→Fe dative interaction to attenuate the Ni(0) electron density. The reduced Ni(0)Fe(II) species mediated the formal two-electron reduction of CO2 to CO, providing a Ni-CO adduct and CO32- as products. During the reaction, an intermediate was observed that is proposed to be a Ni-CO2 species.",

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AU - Gagliardi, Laura

AU - Lu, Connie C.

PY - 2020/10/5

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N2 - Nature utilizes multimetallic sites in metalloenzymes to enable multielectron chemical transformations at ambient conditions and low overpotentials. One such example of multimetallic cooperativity can be found in the C-cluster of Ni-carbon monoxide dehydrogenase (CODH), which interconverts CO and CO2. Toward a potential functional model of the C-cluster, a family of Ni-Fe bimetallic complexes was synthesized that contain direct metal-metal bonding interactions. The complexes were characterized by X-ray crystallography, various spectroscopies (NMR, EPR, UV-vis, Mössbauer), and theoretical calculations. The Ni-Fe bimetallic system has a reversible Fe(III)/Fe(II) redox couple at -2.10 V (vs Fc+/Fc). The Fe-based "redox switch"can turn on CO2 reactivity at the Ni(0) center by leveraging the Ni→Fe dative interaction to attenuate the Ni(0) electron density. The reduced Ni(0)Fe(II) species mediated the formal two-electron reduction of CO2 to CO, providing a Ni-CO adduct and CO32- as products. During the reaction, an intermediate was observed that is proposed to be a Ni-CO2 species.

AB - Nature utilizes multimetallic sites in metalloenzymes to enable multielectron chemical transformations at ambient conditions and low overpotentials. One such example of multimetallic cooperativity can be found in the C-cluster of Ni-carbon monoxide dehydrogenase (CODH), which interconverts CO and CO2. Toward a potential functional model of the C-cluster, a family of Ni-Fe bimetallic complexes was synthesized that contain direct metal-metal bonding interactions. The complexes were characterized by X-ray crystallography, various spectroscopies (NMR, EPR, UV-vis, Mössbauer), and theoretical calculations. The Ni-Fe bimetallic system has a reversible Fe(III)/Fe(II) redox couple at -2.10 V (vs Fc+/Fc). The Fe-based "redox switch"can turn on CO2 reactivity at the Ni(0) center by leveraging the Ni→Fe dative interaction to attenuate the Ni(0) electron density. The reduced Ni(0)Fe(II) species mediated the formal two-electron reduction of CO2 to CO, providing a Ni-CO adduct and CO32- as products. During the reaction, an intermediate was observed that is proposed to be a Ni-CO2 species.

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Bioinspired Nickel Complexes Supported by an Iron Metalloligand

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