Electronic structure analysis and reactivity of the bimetallic bis-titanocene vinylcarboxylate complex, [(Cp2Ti)2(O2C3TMS2)]

Daniel N. Huh; Asim Maity; Gerard P. Van Trieste; Nathan D. Schley; David C. Powers; Ian A. Tonks

doi:10.1016/j.poly.2021.115368

Electronic structure analysis and reactivity of the bimetallic bis-titanocene vinylcarboxylate complex, [(Cp₂Ti)₂(O₂C₃TMS₂)]

Daniel N. Huh, Asim Maity, Gerard P. Van Trieste, Nathan D. Schley, David C. Powers, Ian A. Tonks

Chemistry (Twin Cities)

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

3 Scopus citations

Abstract

Multimetallic redox cooperativity features heavily in both bioinorganic and synthetic reactions. Here, the electronic structure of the bimetallic Ti/Ti complex 11, [(Cp₂Ti)₂(O₂C₃TMS₂)] has been revisited with EPR, confirming a predominantly Ti^III/Ti^III electronic structure. Reactions of 11 with 2,6-dimethylphenyl isocyanide (CNXyl), TMSCl, MeI, and BnCl were explored, revealing differential redox chemistry of the bimetallic core. In reactions with CNXyl and TMSCl, the metallacyclic Ti^III center remained unperturbed, with reactions taking place at the pendent κ²(O,O)-titanocene fragment, while reaction with MeI resulted in remote oxidation of the metallacyclic Ti center, indicative of a cooperative redox process. All structures were studied via X-ray diffraction and EPR spectroscopic analysis, and their electronic structures are discussed in the context of the covalent bond classification (CBC) electron counting method.

Original language	English (US)
Article number	115368
Journal	Polyhedron
Volume	207
DOIs	https://doi.org/10.1016/j.poly.2021.115368
State	Published - Oct 1 2021

Bibliographical note

Funding Information:
Financial support was provided by the National Institutes of Health (R35GM119457), the Alfred P. Sloan Foundation (I. A. T. is a 2017 Sloan Fellow), and the Welch Foundation to D. C. P. (A-1907). Additional support was provided by the National Institute of General Medicine Sciences of the National Institutes of Health to D. N. H from the Ruth L. Kirschstein NRSA Postdoctoral Fellowship (F32GM137547). Instrumentation for the University of Minnesota Chemistry NMR facility was supported from a grant through the National Institutes of Health (S10OD011952). X-ray diffraction experiments were performed with a diffractometer purchased through a grant from NSF/MRI (1229400) and the University of Minnesota. We also thank Dr. Victor G. Young Jr. and Margaret C. Clapham of the University of Minnesota X-ray Crystallographic Laboratory for their assistance with SC-XRD.

Funding Information:
Financial support was provided by the National Institutes of Health (R35GM119457), the Alfred P. Sloan Foundation (I. A. T. is a 2017 Sloan Fellow), and the Welch Foundation to D. C. P. (A-1907). Additional support was provided by the National Institute of General Medicine Sciences of the National Institutes of Health to D. N. H from the Ruth L. Kirschstein NRSA Postdoctoral Fellowship (F32GM137547). Instrumentation for the University of Minnesota Chemistry NMR facility was supported from a grant through the National Institutes of Health (S10OD011952). X-ray diffraction experiments were performed with a diffractometer purchased through a grant from NSF/MRI (1229400) and the University of Minnesota. We also thank Dr. Victor G. Young Jr. and Margaret C. Clapham of the University of Minnesota X-ray Crystallographic Laboratory for their assistance with SC-XRD.

Publisher Copyright:
© 2021 Elsevier Ltd

Keywords

Covalent bond classification
EPR
Oxidation states
Titanium
X-ray

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title = "Electronic structure analysis and reactivity of the bimetallic bis-titanocene vinylcarboxylate complex, [(Cp2Ti)2(O2C3TMS2)]",

abstract = "Multimetallic redox cooperativity features heavily in both bioinorganic and synthetic reactions. Here, the electronic structure of the bimetallic Ti/Ti complex 11, [(Cp2Ti)2(O2C3TMS2)] has been revisited with EPR, confirming a predominantly TiIII/TiIII electronic structure. Reactions of 11 with 2,6-dimethylphenyl isocyanide (CNXyl), TMSCl, MeI, and BnCl were explored, revealing differential redox chemistry of the bimetallic core. In reactions with CNXyl and TMSCl, the metallacyclic TiIII center remained unperturbed, with reactions taking place at the pendent κ2(O,O)-titanocene fragment, while reaction with MeI resulted in remote oxidation of the metallacyclic Ti center, indicative of a cooperative redox process. All structures were studied via X-ray diffraction and EPR spectroscopic analysis, and their electronic structures are discussed in the context of the covalent bond classification (CBC) electron counting method.",

keywords = "Covalent bond classification, EPR, Oxidation states, Titanium, X-ray",

author = "Huh, {Daniel N.} and Asim Maity and {Van Trieste}, {Gerard P.} and Schley, {Nathan D.} and Powers, {David C.} and Tonks, {Ian A.}",

note = "Funding Information: Financial support was provided by the National Institutes of Health (R35GM119457), the Alfred P. Sloan Foundation (I. A. T. is a 2017 Sloan Fellow), and the Welch Foundation to D. C. P. (A-1907). Additional support was provided by the National Institute of General Medicine Sciences of the National Institutes of Health to D. N. H from the Ruth L. Kirschstein NRSA Postdoctoral Fellowship (F32GM137547). Instrumentation for the University of Minnesota Chemistry NMR facility was supported from a grant through the National Institutes of Health (S10OD011952). X-ray diffraction experiments were performed with a diffractometer purchased through a grant from NSF/MRI (1229400) and the University of Minnesota. We also thank Dr. Victor G. Young Jr. and Margaret C. Clapham of the University of Minnesota X-ray Crystallographic Laboratory for their assistance with SC-XRD. Funding Information: Financial support was provided by the National Institutes of Health (R35GM119457), the Alfred P. Sloan Foundation (I. A. T. is a 2017 Sloan Fellow), and the Welch Foundation to D. C. P. (A-1907). Additional support was provided by the National Institute of General Medicine Sciences of the National Institutes of Health to D. N. H from the Ruth L. Kirschstein NRSA Postdoctoral Fellowship (F32GM137547). Instrumentation for the University of Minnesota Chemistry NMR facility was supported from a grant through the National Institutes of Health (S10OD011952). X-ray diffraction experiments were performed with a diffractometer purchased through a grant from NSF/MRI (1229400) and the University of Minnesota. We also thank Dr. Victor G. Young Jr. and Margaret C. Clapham of the University of Minnesota X-ray Crystallographic Laboratory for their assistance with SC-XRD. Publisher Copyright: {\textcopyright} 2021 Elsevier Ltd",

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AU - Maity, Asim

AU - Van Trieste, Gerard P.

AU - Schley, Nathan D.

AU - Powers, David C.

AU - Tonks, Ian A.

N1 - Funding Information: Financial support was provided by the National Institutes of Health (R35GM119457), the Alfred P. Sloan Foundation (I. A. T. is a 2017 Sloan Fellow), and the Welch Foundation to D. C. P. (A-1907). Additional support was provided by the National Institute of General Medicine Sciences of the National Institutes of Health to D. N. H from the Ruth L. Kirschstein NRSA Postdoctoral Fellowship (F32GM137547). Instrumentation for the University of Minnesota Chemistry NMR facility was supported from a grant through the National Institutes of Health (S10OD011952). X-ray diffraction experiments were performed with a diffractometer purchased through a grant from NSF/MRI (1229400) and the University of Minnesota. We also thank Dr. Victor G. Young Jr. and Margaret C. Clapham of the University of Minnesota X-ray Crystallographic Laboratory for their assistance with SC-XRD. Funding Information: Financial support was provided by the National Institutes of Health (R35GM119457), the Alfred P. Sloan Foundation (I. A. T. is a 2017 Sloan Fellow), and the Welch Foundation to D. C. P. (A-1907). Additional support was provided by the National Institute of General Medicine Sciences of the National Institutes of Health to D. N. H from the Ruth L. Kirschstein NRSA Postdoctoral Fellowship (F32GM137547). Instrumentation for the University of Minnesota Chemistry NMR facility was supported from a grant through the National Institutes of Health (S10OD011952). X-ray diffraction experiments were performed with a diffractometer purchased through a grant from NSF/MRI (1229400) and the University of Minnesota. We also thank Dr. Victor G. Young Jr. and Margaret C. Clapham of the University of Minnesota X-ray Crystallographic Laboratory for their assistance with SC-XRD. Publisher Copyright: © 2021 Elsevier Ltd

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N2 - Multimetallic redox cooperativity features heavily in both bioinorganic and synthetic reactions. Here, the electronic structure of the bimetallic Ti/Ti complex 11, [(Cp2Ti)2(O2C3TMS2)] has been revisited with EPR, confirming a predominantly TiIII/TiIII electronic structure. Reactions of 11 with 2,6-dimethylphenyl isocyanide (CNXyl), TMSCl, MeI, and BnCl were explored, revealing differential redox chemistry of the bimetallic core. In reactions with CNXyl and TMSCl, the metallacyclic TiIII center remained unperturbed, with reactions taking place at the pendent κ2(O,O)-titanocene fragment, while reaction with MeI resulted in remote oxidation of the metallacyclic Ti center, indicative of a cooperative redox process. All structures were studied via X-ray diffraction and EPR spectroscopic analysis, and their electronic structures are discussed in the context of the covalent bond classification (CBC) electron counting method.

AB - Multimetallic redox cooperativity features heavily in both bioinorganic and synthetic reactions. Here, the electronic structure of the bimetallic Ti/Ti complex 11, [(Cp2Ti)2(O2C3TMS2)] has been revisited with EPR, confirming a predominantly TiIII/TiIII electronic structure. Reactions of 11 with 2,6-dimethylphenyl isocyanide (CNXyl), TMSCl, MeI, and BnCl were explored, revealing differential redox chemistry of the bimetallic core. In reactions with CNXyl and TMSCl, the metallacyclic TiIII center remained unperturbed, with reactions taking place at the pendent κ2(O,O)-titanocene fragment, while reaction with MeI resulted in remote oxidation of the metallacyclic Ti center, indicative of a cooperative redox process. All structures were studied via X-ray diffraction and EPR spectroscopic analysis, and their electronic structures are discussed in the context of the covalent bond classification (CBC) electron counting method.

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KW - Oxidation states

KW - Titanium

KW - X-ray

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