Bioinspired Nickel Complexes Supported by an Iron Metalloligand

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

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

18 Scopus citations

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

Bibliographical note

Funding Information:
The authors thank Prof. John Lipscomb for access to the EPR spectrometer, J.T. Moore and Michael Dorantes for collecting EPR spectra, Bernd Mienert and Dr. Peter Solheid for collecting the Mössbauer spectra, and Dr. Victor G. Young, Jr. for assistance with X-ray crystallography. J.R.P. was supported by the National Science Foundation (NSF) Graduate Research Fellowship Program. The synthetic work was supported by NSF (CHE-1800110). X-ray diffraction experiments were performed using a crystal diffractometer purchased through a grant from NSF (MRI-1229400) and the University of Minnesota. The computational work was supported by NSF (CHE-1746186). The computational resources were provided by the Minnesota Supercomputing Institute (MSI) at the University of Minnesota.

Publisher Copyright:
© 2020 American Chemical Society.

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access

10.1021/acs.inorgchem.0c02041

OpenUrl availability

Full text

Cite this

@article{cb6b398bbaab44559d13394327c25f9c,

title = "Bioinspired Nickel Complexes Supported by an Iron Metalloligand",

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.",

author = "Prat, {Jacob R.} and Gaggioli, {Carlo A.} and Cammarota, {Ryan C.} and Eckhard Bill and Laura Gagliardi and Lu, {Connie C.}",

note = "Funding Information: The authors thank Prof. John Lipscomb for access to the EPR spectrometer, J.T. Moore and Michael Dorantes for collecting EPR spectra, Bernd Mienert and Dr. Peter Solheid for collecting the M{\"o}ssbauer spectra, and Dr. Victor G. Young, Jr. for assistance with X-ray crystallography. J.R.P. was supported by the National Science Foundation (NSF) Graduate Research Fellowship Program. The synthetic work was supported by NSF (CHE-1800110). X-ray diffraction experiments were performed using a crystal diffractometer purchased through a grant from NSF (MRI-1229400) and the University of Minnesota. The computational work was supported by NSF (CHE-1746186). The computational resources were provided by the Minnesota Supercomputing Institute (MSI) at the University of Minnesota. Publisher Copyright: {\textcopyright} 2020 American Chemical Society.",

year = "2020",

month = oct,

day = "5",

doi = "10.1021/acs.inorgchem.0c02041",

language = "English (US)",

volume = "59",

pages = "14251--14262",

journal = "Inorganic chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "19",

}

TY - JOUR

T1 - Bioinspired Nickel Complexes Supported by an Iron Metalloligand

AU - Prat, Jacob R.

AU - Gaggioli, Carlo A.

AU - Cammarota, Ryan C.

AU - Bill, Eckhard

AU - Gagliardi, Laura

AU - Lu, Connie C.

N1 - Funding Information: The authors thank Prof. John Lipscomb for access to the EPR spectrometer, J.T. Moore and Michael Dorantes for collecting EPR spectra, Bernd Mienert and Dr. Peter Solheid for collecting the Mössbauer spectra, and Dr. Victor G. Young, Jr. for assistance with X-ray crystallography. J.R.P. was supported by the National Science Foundation (NSF) Graduate Research Fellowship Program. The synthetic work was supported by NSF (CHE-1800110). X-ray diffraction experiments were performed using a crystal diffractometer purchased through a grant from NSF (MRI-1229400) and the University of Minnesota. The computational work was supported by NSF (CHE-1746186). The computational resources were provided by the Minnesota Supercomputing Institute (MSI) at the University of Minnesota. Publisher Copyright: © 2020 American Chemical Society.

PY - 2020/10/5

Y1 - 2020/10/5

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.

UR - http://www.scopus.com/inward/record.url?scp=85092039667&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85092039667&partnerID=8YFLogxK

U2 - 10.1021/acs.inorgchem.0c02041

DO - 10.1021/acs.inorgchem.0c02041

M3 - Article

C2 - 32954721

AN - SCOPUS:85092039667

SN - 0020-1669

VL - 59

SP - 14251

EP - 14262

JO - Inorganic chemistry

JF - Inorganic chemistry

IS - 19

ER -

Bioinspired Nickel Complexes Supported by an Iron Metalloligand

Abstract

Bibliographical note

UN SDGs

Access

OpenUrl availability

Other files and links

Fingerprint

Cite this