H. Vanderheijden et B. Hessen, INTERMOLECULAR C-H ACTIVATION BY REACTIVE TITANOCENE ALKYLIDENE INTERMEDIATES, Journal of the Chemical Society, Chemical Communications, (2), 1995, pp. 145-146
Thermal alpha-H abstraction from (C(5)H(4)R)(2)Ti(CH(2)CMe(3))(2) (R =
H, Me) produces reactive titanocene neopentylidene intermediates unde
r mild conditions, that can either be trapped with PMe(3) to yield the
alkylidene complexes (C(5)H(4)R)(2)Ti(CHCMe(3))PMe(3), or add C-H bon
ds of hydrocarbon substrates R'H (R'H = benzene, p-xylene) to the Ti=C
double bond to produce (C(5)H(4)R)(2)Ti(CH(2)CMe(3))R'; an alternativ
e reaction pathway, insertion of the alkylidene moiety into the cyclop
entadienyl C-C bond, has been observed in the presence of THF.