Add time:08/23/2019         Source:sciencedirect.com

CO2 reacts with hexyne(−3) in a catalytic reaction under formation of tetraethyl-2-pyrone, when the catalytic system alkyl3P/acetonitrile/nickel(0) is used. The selectivity of this homogeneous-catalytic reaction can be increased to values of 96% when phosphanes of high basicity and small cone angle are used.The investigation of the system Ni(COD)2/tricyclohexylphosphane/acetonitrile shows that acetonitrile can act as ligand in complexes of nickel(0). A yellow-brown tetranuclear complex was isolated, the structure of which was determined by X-ray diffraction studies. Acetonitrile acts as bridging ligand and is coordinated alkyne-analogously to one nickel center with its triple bond. The free electron pair of the nitrogen atom is bonded to a second nickel atom. Some reaction steps of this selective catalytic reaction are discussed.This reaction represents the first example of a selective homogeneous-catalytic co-oligomerization between CO2 and an unsaturated substrate which takes place under CC linkage with a 3d-transition metal.

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