Enhanced Electrophilicity of Heterobimetallic Bi-Rh Paddlewheel Carbene Complexes: A Combined Experimental, Spectroscopic, and Computational Study

Journal of the American Chemical Society
Lee R CollinsAlois Fürstner

Abstract

Dirhodium paddlewheel complexes are indispensable tools in modern organometallic catalysis for the controlled decomposition of diazo-compounds. Tuning the reactivity of the thus-formed transient carbenes remains an active and dynamic field of research. Herein, we present our findings that the distal metal center plays an as yet underappreciated role in modulating this reactivity. Replacement of one rhodium atom in the bimetallic core for bismuth results in the formation of a significantly more electrophilic carbene complex. Bismuth-rhodium catalysts thereby facilitate previously unknown modes of reactivity for α-diazoester compounds, including the cyclopropanation of alkenes as electron deficient as trichloroethylene. While dirhodium paddlewheel complexes remain the catalysts of choice for many carbene-mediated transformations, their bismuth-rhodium analogues exhibit complementary reactivity and show great potential for small molecule and solvent activation chemistry. DFT calculations highlight the importance of metal-metal bonding interactions in controlling carbene electrophilicity. The paucity of these interactions between the 4d orbitals of rhodium and the 6p orbitals of bismuth results in weaker π-back-bonding interactions...Continue Reading

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Citations

Feb 12, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Takefumi YoshidaMasahiro Yamashita
Apr 19, 2019·Angewandte Chemie·Alexander G TskhovrebovAlois Fürstner
Jan 21, 2020·Chemical Society Reviews·Dong ZhuShifa Zhu
Jan 10, 2020·Chemistry : a European Journal·Michael BuchsteinerAlois Fürstner
Aug 10, 2020·Angewandte Chemie·Benjamin D BergstromLucas W Souza
Nov 5, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Derek CressyAmpofo Darko
Apr 9, 2021·Journal of the American Chemical Society·Santanu SinghaAlois Fürstner
May 20, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Jacqueline Ramler, Crispin Lichtenberg
Mar 1, 2019·Journal of the American Chemical Society·Feng WangJosep Cornella
Jun 27, 2020·Organic Process Research & Development·Elisa Martínez-CastroAbraham Mendoza

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