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Does Reduction-Induced Isomerization of a Uranium(III) Aryl Complex Proceed via C–H Oxidative Addition and Reductive Elimination across the Uranium(II/IV) Redox Couple?

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Does Reduction-Induced Isomerization of a Uranium(III) Aryl Complex Proceed via C–H Oxidative Addition and Reductive Elimination across the Uranium(II/IV) Redox Couple? / Boreen, Michael A.; Ye, Christopher Z.; Kerridge, Andrew et al.
In: Inorganic Chemistry, Vol. 61, No. 23, 13.06.2022, p. 8955-8965.

Research output: Contribution to Journal/Magazine › Journal article › peer-review

Harvard

Boreen, MA, Ye, CZ, Kerridge, A, McCabe, KN, Skeel, BA, Maron, L & Arnold, J 2022, 'Does Reduction-Induced Isomerization of a Uranium(III) Aryl Complex Proceed via C–H Oxidative Addition and Reductive Elimination across the Uranium(II/IV) Redox Couple?', Inorganic Chemistry, vol. 61, no. 23, pp. 8955-8965. https://doi.org/10.1021/acs.inorgchem.2c01563

APA

Boreen, M. A., Ye, C. Z., Kerridge, A., McCabe, K. N., Skeel, B. A., Maron, L., & Arnold, J. (2022). Does Reduction-Induced Isomerization of a Uranium(III) Aryl Complex Proceed via C–H Oxidative Addition and Reductive Elimination across the Uranium(II/IV) Redox Couple? Inorganic Chemistry, 61(23), 8955-8965. https://doi.org/10.1021/acs.inorgchem.2c01563

Vancouver

Boreen MA, Ye CZ, Kerridge A, McCabe KN, Skeel BA, Maron L et al. Does Reduction-Induced Isomerization of a Uranium(III) Aryl Complex Proceed via C–H Oxidative Addition and Reductive Elimination across the Uranium(II/IV) Redox Couple? Inorganic Chemistry. 2022 Jun 13;61(23):8955-8965. Epub 2022 Jun 2. doi: 10.1021/acs.inorgchem.2c01563

Author

Boreen, Michael A. ; Ye, Christopher Z. ; Kerridge, Andrew et al. / Does Reduction-Induced Isomerization of a Uranium(III) Aryl Complex Proceed via C–H Oxidative Addition and Reductive Elimination across the Uranium(II/IV) Redox Couple?. In: Inorganic Chemistry. 2022 ; Vol. 61, No. 23. pp. 8955-8965.

Bibtex

@article{6822c700bcf74179b5eb1162456a100a,
title = "Does Reduction-Induced Isomerization of a Uranium(III) Aryl Complex Proceed via C–H Oxidative Addition and Reductive Elimination across the Uranium(II/IV) Redox Couple?",
abstract = "Reaction of the uranium(III) bis(amidinate) aryl complex {TerphC(NiPr)2}2U(Terph) (2, where Terph = 4,4″-di-tert-butyl-m-terphenyl-2′-yl) with a strong reductant enabled isolation of isomeric uranium(III) bis(amidinate) aryl product {TerphC(NiPr)2}2U(Terph*) (3, where Terph* = 4,4″-di-tert-butyl-m-terphenyl-4′-yl). In terms of connectivity, 3 differs from 2 only in the positions of the U–C and C–H bonds on the central aryl ring of the m-terphenyl-based ligand. A deuterium labeling study ruled out mechanisms for this isomerization involving intermolecular abstraction or deprotonation of the ligand C–H bonds activated during the reaction. Due to the complexity of this rapid, heterogeneous reaction, experimental studies could not further distinguish between two different intramolecular C–H activation mechanisms. However, high-level computational studies were consistent with a mechanism that included two sets of unimolecular, mononuclear C–H oxidative addition and reductive elimination steps involving uranium(II/IV).",
keywords = "Inorganic Chemistry, Physical and Theoretical Chemistry",
author = "Boreen, {Michael A.} and Ye, {Christopher Z.} and Andrew Kerridge and McCabe, {Karl N.} and Skeel, {Brighton A.} and Laurent Maron and John Arnold",
year = "2022",
month = jun,
day = "13",
doi = "10.1021/acs.inorgchem.2c01563",
language = "English",
volume = "61",
pages = "8955--8965",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "23",

}

RIS

TY - JOUR

T1 - Does Reduction-Induced Isomerization of a Uranium(III) Aryl Complex Proceed via C–H Oxidative Addition and Reductive Elimination across the Uranium(II/IV) Redox Couple?

AU - Boreen, Michael A.

AU - Ye, Christopher Z.

AU - Kerridge, Andrew

AU - McCabe, Karl N.

AU - Skeel, Brighton A.

AU - Maron, Laurent

AU - Arnold, John

PY - 2022/6/13

Y1 - 2022/6/13

N2 - Reaction of the uranium(III) bis(amidinate) aryl complex {TerphC(NiPr)2}2U(Terph) (2, where Terph = 4,4″-di-tert-butyl-m-terphenyl-2′-yl) with a strong reductant enabled isolation of isomeric uranium(III) bis(amidinate) aryl product {TerphC(NiPr)2}2U(Terph*) (3, where Terph* = 4,4″-di-tert-butyl-m-terphenyl-4′-yl). In terms of connectivity, 3 differs from 2 only in the positions of the U–C and C–H bonds on the central aryl ring of the m-terphenyl-based ligand. A deuterium labeling study ruled out mechanisms for this isomerization involving intermolecular abstraction or deprotonation of the ligand C–H bonds activated during the reaction. Due to the complexity of this rapid, heterogeneous reaction, experimental studies could not further distinguish between two different intramolecular C–H activation mechanisms. However, high-level computational studies were consistent with a mechanism that included two sets of unimolecular, mononuclear C–H oxidative addition and reductive elimination steps involving uranium(II/IV).

AB - Reaction of the uranium(III) bis(amidinate) aryl complex {TerphC(NiPr)2}2U(Terph) (2, where Terph = 4,4″-di-tert-butyl-m-terphenyl-2′-yl) with a strong reductant enabled isolation of isomeric uranium(III) bis(amidinate) aryl product {TerphC(NiPr)2}2U(Terph*) (3, where Terph* = 4,4″-di-tert-butyl-m-terphenyl-4′-yl). In terms of connectivity, 3 differs from 2 only in the positions of the U–C and C–H bonds on the central aryl ring of the m-terphenyl-based ligand. A deuterium labeling study ruled out mechanisms for this isomerization involving intermolecular abstraction or deprotonation of the ligand C–H bonds activated during the reaction. Due to the complexity of this rapid, heterogeneous reaction, experimental studies could not further distinguish between two different intramolecular C–H activation mechanisms. However, high-level computational studies were consistent with a mechanism that included two sets of unimolecular, mononuclear C–H oxidative addition and reductive elimination steps involving uranium(II/IV).

KW - Inorganic Chemistry

KW - Physical and Theoretical Chemistry

U2 - 10.1021/acs.inorgchem.2c01563

DO - 10.1021/acs.inorgchem.2c01563

M3 - Journal article

VL - 61

SP - 8955

EP - 8965

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 23

ER -