Recently our group has discovered that (iPrPNP)Mn(CO)2 (PNP = [N{CH2CH2(PiPr2)}2]-) is capable of performing the 1,2-addition of many H-X substrates across the Mn-amide bond. Of particular interest was the 1,2-addition of H2O, resulting in the formation of a rare, mononuclear, manganese-hydroxide complex, (iPrPNHP)Mn(OH)(CO)2. We have begun to study analogous chemistry with Ni. In this talk, we will discuss the synthesis and characterization of a series of (iPrPNP)-Ni complexes leading to the formation of [(iPrPNP)Ni(PMe3)][BPh4]. This cationic complex was the focus of studies of salt metathesis and 1,2-addition reactions, leading to the formation of Ni-OH and Ni-NHR complexes. Despite being a cation, the compound, [(iPrPNHP)Ni(OH)][BPh4], has a nucleophilic hydroxide ligand that allows it to react with unsaturated electrophiles such as nitriles. This reactivity as well as the electronic structure of this class of compounds will be discussed.

Addition of HX across Ni amide bonds: Synthesis and reactivity of Ni hydroxide complexes

254th National Meeting (2017)

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