Sterically controlled silacycloalkyl diamide complexes of titanium(IV): Synthesis, structure, and catalytic behavior of (cycl)Si(NBut)(2)TiCl2 [(cycl)Si = silacyclobutane, silacyclopentane, silacyclopentene, and silacyclohexane]

The chemistry of titanium complexes stabilized by a series of cyclic silyld iamide ligands (cycl)Si(HNBut)(2) (2) derived from the silacycloalkyl unit -(CH2)(n)Si-, with n = 3, 4, and 5, has been studied. Thus, a variety of sp iro-siladiazatitanacyclobutane complexes (cycl)Si(NBut)(2)TiCl2 (3) has bee n prepared by the reaction of the dilithium salt of 2 with titanium tetrach loride. The reaction of 2 with Ti(NMe2)(4) in refluxing toluene yields (cyc l)Si(NBut)(2)Ti(NMe2)(2) (4), and the product 4 is converted to 3 in a mode rate isolated yield by treatment with excess Me3SiCl. Dimethyl complexes of the type (cycl)Si(NBut)(2)TiMe2 (5) were prepared by the reaction of 3 wit h MeMgBr. Complexes 3 have been characterized by X-ray crystallography. As a result of the formation of the siladiazatitanacyclobutane ring, the titan ium atoms in 3 exhibit distorted-tetrahedral configurations with the two ch loride ligands. in addition, the crystallographic results establish that st eric interactions between the silacycloalkyl and tert-butyl groups influenc e the C(Bu-t)-N-Ti angles and, hence, the steric environment at titanium. T he compounds 3 were further investigated as potential catalysts for the pol ymerization of ethylene. While sterically less demanding silacyclobutyl and -pentyl diamide complexes (3a and 3b) exhibit low ethylene polymerization activity (4.0-5.8 kg PE mol(cat)(-1) h(-1)) in the presence of methylalumox ane, the highly puckered silacyclohexyl diamide complex 3c shows better act ivity (14 kg PE mol(cat)(-1) h(-1)) for ethylene polymerization when it is activated with MAO.