Selective propylene dimerization to 2,3-dimethylbutenes by homogeneous catalysts prepared by oxidative addition of alpha-nitroketones to nickel(0) complexes in the presence of phosphine ligands and organoaluminium co-catalysts

Novel nickel catalysts, prepared in situ by oxidative: addition of alpha -n itroketones to nickel(O) complexes, in the presence of a phophine ancillary ligand and activated by organoaluminium co-catalysts were investigated in propylene oligomerization with the aim to selectively obtain 2,3-dimethylbu tenes (DMB). In particular, the effect of the nature of the alpha -nitroket onate ligand as well as of the basicity and bulkiness of the phosphine on c atalyst performances were studied. Finally, the influence of the type of or ganoaluminium co-catalyst and reaction temperature were examined. In particular, when the Ni(cod)(2)/tricyclohexylphosphine (PCy3)/alpha -nit roacetophenone (naph)/methylalumoxane (MAO) catalytic system was employed, the highest up to now reported regioselectivity within C-6 cut (>90%) was a chieved. Moreover, the use of balanced mixtures of MAO and Et2AlCl allowed to optimize the catalyst performances up to an overall yield to DMB of almo st 70%, a significant productivity being also achieved (TOF = 4500 h(-1)). (C) 2001 Elsevier Science B.V. All rights reserved.