Solvent-Dependent Carbon-to-Metal Hydrogen Atom Transfer Reactivity of a Square Planar Rhodium(II) Alkynyl Complex
Abstract
We report on the synthesis and characterization of the square planar rhodium(II) alkynyl complex [Rh(PNP-tBu)(C equivalent to 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 equivalent to CtBu)]⁺ has been substantiated experimentally. Study of [Rh(PNP-tBu)(C equivalent to 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 alpha,alpha,alpha-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.
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BibTeX
@article{hood2026solventdependent,
title = {{Solvent-Dependent Carbon-to-Metal Hydrogen Atom Transfer Reactivity of a Square Planar Rhodium(II) Alkynyl Complex}},
author = {Thomas M. Hood and Sophie H. Dewick and John, Anjali and Jeremiah P. Tidey and Julie V. Macpherson and Ragnar Björnsson and Emma Richards and Tobias Krämer and Adrian B. Chaplin},
journal = {Organometallics},
year = {2026},
month = oct,
doi = {10.1021/acs.organomet.6c00053},
url = {https://hal.science/hal-05591564v1},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Solvent-Dependent Carbon-to-Metal Hydrogen Atom Transfer Reactivity of a Square Planar Rhodium(II) Alkynyl Complex
AU - Thomas M. Hood
AU - Sophie H. Dewick
AU - John, Anjali
AU - Jeremiah P. Tidey
AU - Julie V. Macpherson
AU - Ragnar Björnsson
AU - Emma Richards
AU - Tobias Krämer
AU - Adrian B. Chaplin
PY - 2026
DA - 2026/10/06
JO - Organometallics
DO - 10.1021/acs.organomet.6c00053
UR - https://hal.science/hal-05591564v1
AB - We report on the synthesis and characterization of the square planar rhodium(II) alkynyl complex [Rh(PNP-tBu)(C equivalent to 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 equivalent to CtBu)]⁺ has been substantiated experimentally. Study of [Rh(PNP-tBu)(C equivalent to 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 alpha,alpha,alpha-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.
SN - 0276-7333
SN - 1520-6041
ER -