Thermal decomposition of the carbyl compounds {C5H4(CH2)(2)NR}TiR'(2) proceeds through alpha- and beta-H elimination to give stable aryne, alkylidene, and olefin. complexes in the presence of PMe3. Reaction of the dibenzyl compound {C5H4(CH2)(2)N-t-Bu}Ti(CH2Ph)(2) with B(C6F5)(3) gives the cationic [{C5H4(CH2)(2)N-t-Bu}TiCH2Ph](+), which is an active catalyst for the polymerization of ethene and propene.