Carbon-hydrogen bond activation, C-N bond coupling, and cycloaddition reactivity of a three-coordinate nickel complex featuring a terminal imido ligand.

ABSTRACT: The three-coordinate imidos (dtbpe)Ni?NR (dtbpe = (t)Bu2PCH2CH2P(t)Bu2, R = 2,6-(i)Pr2C6H3, 2,4,6-Me3C6H2 (Mes), and 1-adamantyl (Ad)), which contain a legitimate Ni-N double bond as well as basic imido nitrogen based on theoretical analysis, readily deprotonate HC?CPh to form the amide acetylide species (dtbpe)Ni{NH(Ar)}(C?CPh). In the case of R = 2,6-(i)Pr2C6H3, reductive carbonylation results in formation of the (dtbpe)Ni(CO)2 along with the N-C coupled product keteneimine PhCH?C?N(2,6- (i)Pr2C6H3). Given the ability of the Ni?N bond to have biradical character as suggested by theoretical analysis, H atom abstraction can also occur in (dtbpe)Ni?N{2,6-(i)Pr2C6H3} when this species is treated with HSn((n)Bu)3. Likewise, the microscopic reverse reaction--conversion of the Ni(I) anilide (dtbpe)Ni{NH(2,6-(i)Pr2C6H3)} to the imido (dtbpe)Ni?N{2,6-(i)Pr2C6H3}--is promoted when using the radical Mes*O(•) (Mes* = 2,4,6-(t)Bu3C6H2). Reactivity studies involving the imido complexes, in particular (dtbpe)Ni?N{2,6-(i)Pr2C6H3}, are also reported with small, unsaturated molecules such as diphenylketene, benzylisocyanate, benzaldehyde, and carbon dioxide, including the formation of C-N and N-N bonds by coupling reactions. In addition to NMR spectroscopic data and combustion analysis, we also report structural studies for all the cycloaddition reactions involving the imido (dtbpe)Ni?N{2,6-(i)Pr2C6H3}.

SUBMITTER: Mindiola DJ 

PROVIDER: S-EPMC4269405 | biostudies-literature | 2014 Dec

REPOSITORIES: biostudies-literature