Issue 5, 2016

Reactions of [Cu(X)(BPEP-Ph)] (X = PF6, SbF6) with silyl compounds. Cooperative bond activation involving non-coordinating anions

Abstract

Bond activation of silyl compounds, assisted by the cooperative action of non-coordinating anions, is achieved using Cu(I) complexes coordinated with a PNP-pincer type phosphaalkene ligand, [Cu(X)(BPEP-Ph)] (X = PF6 (1a), SbF6 (1b); BPEP-Ph = 2,6-bis[1-phenyl-2-(2,4,6-tri-tert-butylphenyl)-2-phosphaethenyl]pyridine). Complexes 1a and 1b react with Me3SiCN to form Me3SiF and Cu(I) cyanide complexes of the formula [Cu(CN-EF5)(BPEP-Ph)] (E = P (2a), Sb (2b)), in which the CN ligand is associated with the EF5 group arising from EF6. Formation of the intermediary isonitrile complex [Cu(CNSiMe3)(BPEP-Ph)]+SbF6 (3b) is confirmed by its isolation. Thus, a two-step reaction process involving coordination of Me3SiCN, followed by nucleophilic attack of SbF6 on the silicon atom of 3b is established for the conversion of 1b to 2b. Complex 1b cleaves the H–Si bond of PhMe2SiH as well. The isolation and structural identification of [Cu(BPEP-Ph)]+BArF4 (1c) (BArF4 = B{3,5-(CF3)2C6H3}4) as a rare example of a T-shaped, three-coordinated Cu(I) complex is reported.

Graphical abstract: Reactions of [Cu(X)(BPEP-Ph)] (X = PF6, SbF6) with silyl compounds. Cooperative bond activation involving non-coordinating anions

Supplementary files

Article information

Article type
Paper
Submitted
17 août 2015
Accepted
25 sept. 2015
First published
25 sept. 2015

Dalton Trans., 2016,45, 2079-2084

Author version available

Reactions of [Cu(X)(BPEP-Ph)] (X = PF6, SbF6) with silyl compounds. Cooperative bond activation involving non-coordinating anions

Y. Nakajima, T. Tsuchimoto, Y. Chang, K. Takeuchi and F. Ozawa, Dalton Trans., 2016, 45, 2079 DOI: 10.1039/C5DT03166D

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