Formation of a nickel carbon dioxide adduct and its transformation mediated by a Lewis acid.

An uncommon nickel dinitrogen adduct and its tendency toward CO2 binding are investigated using a (PP(Me)P)Ni scaffold. (PP(Me)P)Ni(N2) (1) and {(PP(Me)P)Ni}2(μ-N2) (2) were prepared and their treatment with CO2 revealed the formation of (PP(Me)P)Ni(η(2)-CO2) (3). This is a new type of CO2 binding for a zero-valent nickel center supported by three donor ligands, reminiscent of the CODH active site environment. Clear unique structural differences in 3 are evident when compared with previous 4-coordinate Ni-CO2 adducts. Compound 3 when treated with B(C6F5)3 gives the Lewis acid-base adduct (PP(Me)P)Ni{COOB(C6F5)3} (4) possessing a Ni-μ-CO2-κ(2)C,O-B moiety.