A comparative analysis of hydrosilative amide reduction catalyzed by first-row transition metal (Mn, Fe, Co, and Ni) N-phosphinoamidinate complexes. Issue 26 (12th November 2018)

• Record Type: Journal Article
• Authors: Macaulay, Casper M.; Ogawa, Takahiko; McDonald, Robert; Sydora, Orson L.; Stradiotto, Mark; Turculet, Laura
• Is Part Of: Dalton transactions. Volume 48:Issue 26(2019)
• Page Start: 9581
• Page End: 9587
• Publication Date: 2018-11-12
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c8dt04221g
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Screening reveals(PN)Ni(x ) pre-catalysts to be effective for the hydrosilative reduction of amides under mild conditions. Abstract : A comparative study of the performance of(PN)M(N(SiMe3 )2 ) (M = Mn, Fe, Co, and Ni) pre-catalysts supported by N -phosphinoamidinate ligation, as well asM(N(SiMe3 )2 ) n (M = Li, Na, K, Mn, Fe, and Co) pre-catalysts, in the hydrosilative reduction of selected tertiary amide test substrates using PhSiH3 is reported. Encouraged by the performance observed herein for(PN)Ni(N(SiMe3 )2 ) in the reduction of both N, N -dibenzylbenzamide and N, N -diisopropylbenzamide, further competitive testing involving the known complex(PN)Ni(NHdipp) (dipp = 2, 6-diisopropylphenyl), as well as the new and crystallographically characterized mononuclear complexes(PN)Ni(OR) (R = 2, 6-dimethylphenyl or t Bu), revealed(PN)Ni(O t Bu) to be particularly effective in such reduction chemistry, including transformations involving the secondary amides N -benzylbenzamide and caprolactam.