Affiliation:
1. Department of Chemistry Fudan University Shanghai 200433 China
2. State Key Laboratory of Organometallic Chemistry Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences Shanghai 200032 China
Abstract
Comprehensive SummaryTwo‐electron reduction of [N2NBn]TiIVCl2 (3) gave a highly reactive [N2N]TiII species, which underwent C—O bond activation of THF (tetrahydrofuran) to generate [N2NBn]TiIV[O(CH2)4] (4) through oxidative addition. The resulted TiIV–Csp3 bond in oxametallacyclohexane was tantamount to the elaborately‐designed Ti‐alkyl complexes, competent to activate intramolecular Csp2–H bond, forming ortho‐cyclometalated complex [N2NCH2C6H4]TiIV(OnBu) (5). Key intermediates were isolated and fully characterized by X‐ray crystallography. Mechanistic studies revealed that the oxidative addition of C—O bond took place at TiII‐center via a radical intermediate, while a Csp2–H bond activation proceeded by σ‐bond metathesis with a kitelike four‐centered TiIV‐transition state.
Funder
National Natural Science Foundation of China
Cited by
1 articles.
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