OXIDATIVE ADDITION OF ALKANENITRILES TO NICKEL(0) COMPLEXES VIA ?-INTERMEDIATES

Article abstract of DOI:10.1016/S0022-328X(00)98512-7

The alkanenitriles R(C6H5)CHCN (R=H, CH3) coordinate rapidly and quantitatively through the CN group to the complexes or <(Ni(PCy3)2)2N2>.Both the end-on and the edge-on adducts are formed, and are present in an equilibrium the position of which is governed by the amount of added PCy3.The ?-complexes react to give the cyano-organometal complexes through an oxidative addition involving splitting of the C-CN bond.The complexes obtained are unstable and slowly decompose under the reaction conditions to give the coupling R'-R' (R=H) or the β-elimination R'(-H) (R=CH3) products.The kinetics of the reaction and the stereochemical result suggest a template mechanism in agreement with the findings above.