Facile Activation of Triarylboranes by Rhenium(V) Oxo Imido Complexes
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https://figshare.com/articles/dataset/Facile_Activation_of_Triarylboranes_by_Rhenium_V_Oxo_Imido_Complexes/12203195
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资源简介：
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 = 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.
创建时间：
2020-04-27
