Reactions of [Cu(X)(BPEP-Ph)] (X = PF6, SbF6) with silyl compounds. Cooperative bond activation involving non-coordinating anions. Issue 5 (12th October 2015)

• Record Type: Journal Article
• Authors: Nakajima, Yumiko; Tsuchimoto, Takahiro; Chang, Yung-Hung; Takeuchi, Katsuhiko; Ozawa, Fumiyuki
• Is Part Of: Dalton transactions. Volume 45:Issue 5(2016)
• Page Start: 2079
• Page End: 2084
• Publication Date: 2015-10-12
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c5dt03166d
• Languages: English
• ISSNs: 1477-9226

Abstract

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, SbF6 ). 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). Complexes1a and1b react with Me3 SiCN to form Me3 SiF 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 Me3 SiCN, followed by nucleophilic attack of SbF6 − on the silicon atom of3b is established for the conversion of1b to2b . Complex1b cleaves the H–Si bond of PhMe2 SiH as well. The isolation and structural identification of [Cu(BPEP-Ph)] + BAr F 4 − (1c ) (BAr F 4 = B{3, 5-(CF3 )2 C6 H3 }4 ) as a rare example of a T-shaped, three-coordinated Cu(i ) complex is reported.