European Journal of Inorganic Chemistry p. 3195 - 3202 (2018)
Update date:2022-08-11
Topics:
Li, Tongyu
Wang, Zhuo
Liu, Kai
Xing, Siyang
Zhu, Bolin
Reactions of three aryl-substituted phosphines with [Cp*IrCl2]2 afforded the corresponding five-membered or six-membered cyclometalated iridium complexes (2 or 5,6) via an intramolecular C(sp2)–H bond activation. Insertion reactions of the five-membered cycloiridated complex 2 with PhC≡CPh and PhC≡CCOPh resulted in the corresponding five-membered and six-membered doubly cycloiridated complexes 7 and 8, the formation of which presumably went through the vinylidene rearrangement of alkynes followed by 1,1-insertion; while the reactions of the six-membered cyclometalated complexes 5, 6 with PhC≡CPh or PhC≡CCOPh gave the corresponding eight-membered cycloiridated complexes 9–12 by 1,2-insertion. The hydrosilylation of imines catalyzed by five- or six-membered P-containing cycloiridated complexes were studied, and the results proved that the six-membered cycloiridated complex 5 can be used as an efficient catalyst, which was applied for the hydrosilylation of various imines, especially aldimines. Molecular structures of complexes 9, 10 and 12 were determined by X-ray diffraction.
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