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One Electron Changes Everything: Synthesis, Characterization, and Reactivity Studies of [Re(NCCH3)6]3+


Bolliger, Robin; Blacque, Olivier; Braband, Henrik; Alberto, Roger (2022). One Electron Changes Everything: Synthesis, Characterization, and Reactivity Studies of [Re(NCCH3)6]3+. Inorganic Chemistry, 61(46):18325-18334.

Abstract

Oxidation of [Re(NCCH3)6]2+ with the thianthrene radical cation results in the formation of [Re(NCCH3)6]3+, one of the very rare cases of a fully solvated +3 complex. It was fully characterized by spectroscopy and X-ray structure analysis. In contrast to its reduced analogue, [Re(NCCH3)6]3+ exhibits a much faster CH3CN exchange. Hence, substitution reactions proceed at 20 °C within minutes. Its potential as a versatile precursor for ReIII chemistry was examined with a series of substitution reactions. The more lipophilic analogue [Re(NCPh)6]3+ was synthesized by nitrile exchange in benzonitrile (NCPh). The Re(II) analogue of [Re(NCPh)6]3+, [Re(NCPh)6]2+, forms by AgI-mediated oxidation of in situ formed [Re(η6-C6H6)(NCPh3)3]+ in NCPh. The same synthetic strategy is feasible for the synthesis of [Re(NCCH3)6]2+ as well. [Re(NCCH3)6]3+ reacts with 1,4,7-trithiacyclononane (C6H12S3) to yield sevenfold-coordinated [Re(κ3-C6H12S3)2(NCCH3)]3+. The reaction of [Re(NCCH3)6]3+ with 1 equiv of (NBu4)X produces the ReIII monohalide complexes [ReX(NCCH3)5]2+ (X = Cl, Br, I). Mixed ReIII dihalides (trans-[ReXY(NCCH3)4]+) were obtained by treating [ReX(NCCH3)5]2+ with a second equivalent of (NBu4)Y (if X = Cl, Y = Br, I; if X = Br, Y = I). Because of this fast CH3CN exchange, [Re(NCCH3)6]3+ is a very suitable precursor for new ReIII complexes.

Abstract

Oxidation of [Re(NCCH3)6]2+ with the thianthrene radical cation results in the formation of [Re(NCCH3)6]3+, one of the very rare cases of a fully solvated +3 complex. It was fully characterized by spectroscopy and X-ray structure analysis. In contrast to its reduced analogue, [Re(NCCH3)6]3+ exhibits a much faster CH3CN exchange. Hence, substitution reactions proceed at 20 °C within minutes. Its potential as a versatile precursor for ReIII chemistry was examined with a series of substitution reactions. The more lipophilic analogue [Re(NCPh)6]3+ was synthesized by nitrile exchange in benzonitrile (NCPh). The Re(II) analogue of [Re(NCPh)6]3+, [Re(NCPh)6]2+, forms by AgI-mediated oxidation of in situ formed [Re(η6-C6H6)(NCPh3)3]+ in NCPh. The same synthetic strategy is feasible for the synthesis of [Re(NCCH3)6]2+ as well. [Re(NCCH3)6]3+ reacts with 1,4,7-trithiacyclononane (C6H12S3) to yield sevenfold-coordinated [Re(κ3-C6H12S3)2(NCCH3)]3+. The reaction of [Re(NCCH3)6]3+ with 1 equiv of (NBu4)X produces the ReIII monohalide complexes [ReX(NCCH3)5]2+ (X = Cl, Br, I). Mixed ReIII dihalides (trans-[ReXY(NCCH3)4]+) were obtained by treating [ReX(NCCH3)5]2+ with a second equivalent of (NBu4)Y (if X = Cl, Y = Br, I; if X = Br, Y = I). Because of this fast CH3CN exchange, [Re(NCCH3)6]3+ is a very suitable precursor for new ReIII complexes.

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Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Scopus Subject Areas:Physical Sciences > Physical and Theoretical Chemistry
Physical Sciences > Inorganic Chemistry
Uncontrolled Keywords:Inorganic Chemistry, Physical and Theoretical Chemistry
Language:English
Date:21 November 2022
Deposited On:17 Feb 2023 13:53
Last Modified:29 May 2024 01:48
Publisher:American Chemical Society (ACS)
ISSN:0020-1669
OA Status:Green
Free access at:PubMed ID. An embargo period may apply.
Publisher DOI:https://doi.org/10.1021/acs.inorgchem.2c02056
PubMed ID:36169602
  • Content: Published Version
  • Language: English
  • Licence: Creative Commons: Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0)