Radical Capture at Nickel(II) Complexes: C–C, C–N, and C–O Bond Formation
Year: 2020
Type: article
Abstract: The dinuclear b-diketiminato Ni II tert -butoxide {[Me 3 NN]Ni} 2 ( μ -O t Bu) 2 ( 2 ), synthesized from [Me 3 NN]Ni(2,4-lutidine) ( 1 ) and di- tert -butylperoxide, is a versatile precursor for the synthesis of a series of Ni II complexes [Me 3 NN]Ni-FG to illustrate C-C, C-N, and C-O bond formation at Ni II via radicals. {[Me 3 NN]Ni} 2 ( μ -O t Bu) 2 reacts with nitromethane, alkyl and aryl amines, acetophenone, benzamide, ammonia and phenols to deliver corresponding mono- or dinuclear [Me 3 NN]Ni-FG species (FG = O 2 NCH 2 , R-NH, ArNH, PhC(O)NH, PhC(O)CH 2 , NH 2 and OAr). Many of these Ni II complexes are capable of capturing the benzylic radical PhCH(•)CH 3 to deliver corresponding PhCH(FG)CH 3 products featuring C-C, C-N or C-O bonds. DFT studies shed light on the mechanism of these transformations and suggest two competing pathways that depend on the nature of the functional groups. These radical capture reactions at [Ni II ]-FG complexes outline key C-C, C-N, and C-O bond forming steps and suggest new families of nickel radical relay catalysts.
Source: Organometallics
Institution: Georgetown University
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
Award: G26343026
OpenAlex ID: W3023772415