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A silica-supported monomeric alkylaluminum co-catalyst was prepared via Surface Organometallic Chemistry by contacting tris-(neopentyl)aluminum and partially dehydroxylated silica . This system, fully characterized by solid-state 27 Al NMR augmented by computational studies, efficiently activates ( n Bu 3 P) 2 NiCl 2 towards dimerization of ethene demonstrating comparable activity to previously reported dimeric diethylaluminum chloride supported on silica. Three types of aluminum surface species have been identified monografted tetracoord