Facile Activation of Triarylboranes by Rhenium(V) Oxo Imido Complexes.
Inorg Chem
; 59(10): 7216-7226, 2020 May 18.
Article
in En
| MEDLINE
| ID: mdl-32339452
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-ß-diketiminate) with organic azides R-N3 (R = tBu, 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.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
Inorg Chem
Year:
2020
Document type:
Article
Affiliation country:
United States