Hood, Thomas M., Dewick, Sophie H., John, Anjali, Tidey, Jeremiah P., Macpherson, Julie V., Bjornsson, Ragnar, Richards, Emma  ORCID: https://orcid.org/0000-0001-6691-2377, Krämer, Tobias and Chaplin, Adrian B.
2026.
Solvent-dependent carbon-to-metal hydrogen atom transfer reactivity of a square planar rhodium(ii) alkynyl complex.
Organometallics
45
(7)
, pp. 892-901.
10.1021/acs.organomet.6c00053
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Abstract
We report on the synthesis and characterization of the square planar rhodium(II) alkynyl complex [Rh(PNP-tBu)(C≡CtBu)]+ and its transformation into the vinylidene derivative [Rh(PNP-tBu)(C═CHtBu)]+ by reaction with 9,10-dihydroanthracene. Computational analysis supports a mechanism involving carbon-to-metal hydrogen atom transfer followed by 1,3-hydride migration, and intermediate formation of the associated rhodium(III) alkynyl hydride [Rh(PNP-tBu)H(C≡CtBu)]+ has been substantiated experimentally. Study of [Rh(PNP-tBu)(C≡CtBu)]+ in the solid state by EPR spectroscopy, supplemented by multireference CAS(9,6)/NEVPT2 calculations, enabled assignment as a metal-centered radical to be corroborated, while analysis of frozen glass solutions revealed the presence of square pyramidal solvent adducts of tetrahydrofuran, 2-methyltetrahydrofuran, 1,2-difluorobenzene, fluorobenzene, and α,α,α-trifluorotoluene. Consistent with a carbon-to-metal hydrogen atom transfer mechanism, the extent of solvent coordination measured by EPR spectroscopy inversely correlates with the rate at which the metalloradical reacts with 9,10-dihydroanthracene.
| Item Type: | Article |
|---|---|
| Date Type: | Publication |
| Status: | Published |
| Schools: | Schools > Chemistry |
| Publisher: | American Chemical Society |
| ISSN: | 0276-7333 |
| Date of First Compliant Deposit: | 7 April 2026 |
| Date of Acceptance: | 17 March 2026 |
| Last Modified: | 08 May 2026 11:14 |
| URI: | https://orca.cardiff.ac.uk/id/eprint/186204 |
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