Abstract Diphenylneopentylsilene, Ph 2 Si= CHCH 2 t Bu (3), is prepared as a reactive intermediate by the reaction of diphenylvinylchlorosilane (1) with Li t Bu in nonpolar solvents via the α-lithioadduct Ph 2 Si (Cl) CH (Li) CH 2 t Bu (2). This lithiated species can be trapped by trimethylsilyltriflate and yields silene 3 by 1, 2-LiCl-elimination. Without suitable Si= C- trapping agents, the E/Z-isomeric tetraphenyl-2, 4-dineopentyl-1, 3-disilacyclobutane (6) is ...