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Updated: Dec 23, 2025

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
Facile Activation of Triarylboranes by Rhenium(V) Oxo Imido Complexes
Trevor D Lohrey1,2, Emmanuel A Cortes1, Robert G Bergman1
1Department of Chemistry, University of California, Berkeley, California 94720, United States.
Abstract:
We report the synthesis and reactivity studies of a pair of rhenium(V) oxo imido complexes. Oxidation of the rhenium(III) terminal oxo ORe(η2-DHF)(BDI) (DHF = dihydrofulvalene, BDI = N,N'-bis(2,6-diisopropylphenyl)-3,5-dimethyl-β-diketiminate) with organic azides R-N3 (R = Bu, 2,6-diisopropylphenyl) yields the title complexes. Computational studies confirm that the rhenium oxo moieties of these complexes are polarized and correspondingly nucleophilic, owing to the preferential π bonding of the imido ligand to the Re center. This asymmetry in the metal-ligand multiple bond electronic structure facilitates the ready activation of B-C bonds in triarylboranes (BPh3 and B(C6F5)3), yielding rhenium(V) aryl borinate complexes. In the case of BPh3, subsequent cyclometalation of the 1,2-addition products was found to take place upon heating, ejecting benzene to form bidentate diphenylborinate complexes.
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