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The reaction of rhenium nitrosyl with a sterically hindered NHC-carbene


Grieco, G; Blacque, Olivier (2022). The reaction of rhenium nitrosyl with a sterically hindered NHC-carbene. Dalton Transactions, 51(4):1521-1526.

Abstract

In this article, we present the serendipitous synthesis of the unknown Re(I) complex [(OPPh3)Re(NO)2Cl3] (3) that we obtained reacting the Re(V) complex trans-[(PPh3)2ReOCl3] (1) with NO gas in presence of CH3COOH. We found that 3 reacts with 1,3-bis (2,4,6-trimethylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene (IMes) to yield a stable oximate—Re(III) complex [(OPPh3)Re(NO)(ON[double bond, length as m-dash]IMes)Cl3] (4). We speculate that the IMes reacts with a bent NO, because the DFT calculations excluded the formation of both dimeric and η2–NO complexes in solution. The reactivity of the NO toward the carbene is probably due to an internal fluxional process in which the NO passes from linear to bent, triggered by the π-electrons given by the three chlorides to the Re through the mesomeric effect.

Abstract

In this article, we present the serendipitous synthesis of the unknown Re(I) complex [(OPPh3)Re(NO)2Cl3] (3) that we obtained reacting the Re(V) complex trans-[(PPh3)2ReOCl3] (1) with NO gas in presence of CH3COOH. We found that 3 reacts with 1,3-bis (2,4,6-trimethylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene (IMes) to yield a stable oximate—Re(III) complex [(OPPh3)Re(NO)(ON[double bond, length as m-dash]IMes)Cl3] (4). We speculate that the IMes reacts with a bent NO, because the DFT calculations excluded the formation of both dimeric and η2–NO complexes in solution. The reactivity of the NO toward the carbene is probably due to an internal fluxional process in which the NO passes from linear to bent, triggered by the π-electrons given by the three chlorides to the Re through the mesomeric effect.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Uncontrolled Keywords:Inorganic Chemistry
Language:English
Date:1 January 2022
Deposited On:13 Jan 2022 14:15
Last Modified:27 Mar 2024 03:05
Publisher:Royal Society of Chemistry
ISSN:1477-9226
OA Status:Hybrid
Publisher DOI:https://doi.org/10.1039/d1dt03966k
Project Information:
  • : FunderUniversität Zürich
  • : Grant ID
  • : Project Title
  • Content: Published Version
  • Licence: Creative Commons: Attribution 3.0 Unported (CC BY 3.0)