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OXIDATIVE ADDITION OF ALKANENITRILES TO NICKEL(0) COMPLEXES VIA ?-INTERMEDIATES
Favero, Giancarlo,Morvillo, Antonnio,Turco, Aldo
, p. 251 - 258 (2007/10/02)
The alkanenitriles R(C6H5)CHCN (R=H, CH3) coordinate rapidly and quantitatively through the CN group to the complexes or .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.
