18039-90-2Relevant articles and documents
Titanium(III) alkoxy-N-heterocyclic carbenes and a safe, low-cost route to TiCl3(THF)3
Jones, Natalie A.,Liddle, Stephen T.,Wilson, Claire,Arnold, Polly L.
, p. 755 - 757 (2008/10/09)
A new, facile method for the synthesis of [TiCl3-(THF) 3 is reported; THF extraction from the commercially widely available and cheap compound 3TiCl3·AlCl3 affords aluminum-free [TiCl3(THF)3] in excellent yield as a blue microcrystalline solid. Treatment of [TiCl3(THF)3] with 3 equiv of the potassium alkoxy carbene KL[K{OCMe2CH 2(1-C[NCHCH-NPri])}] affords the homoleptic, octahedral Ti(III) tris(carbene) complex [TiL3] in high yield, which is shown to form as the mer-isomer by a single-crystal X-ray diffraction study.
Substituent effects. Synthesis and structural characterization of group 4 metallacarboranes containing (C6H5CH2) 2C2B9H92- and [o-C 6H4(CH2)2]C2B 9H92- ligands
Kwong, Wai-Chuen,Chan, Hoi-Shan,Tang, Yong,Xie, Zuowei
, p. 4301 - 4307 (2008/10/09)
Substituants on the carborane cage carbons affect not only bonding interactions between the group 4 metal ion and the carboranyl of the C 2B9 system but also the reactivity pattern of the resulting metal complexes. Treatment of MCI4(THF)2 with 1 equiv of [(C6H5CH2)2C 2B9H9]Na2(THF),x in THF at room temperature gave the bis(carboranyl) complexes {n4:n 2-[(C6H5CH2)2C 2B9H9]2MCI(THF)}{Na(THF) 3} (M = Zr (1), Hf (2)). Under the same reaction conditions, interaction of TiCl4(THF)2 with 1 equiv of [(C 6H5CH2)2C2B 9H9]Na2(THF)x led to the isolation of a small amount of TiCl3(THF)3 and B-substituted zwitterionic compound (C6H5CH2) 2C2B9H9(THF) (4). Reaction of 1 with 1 equiv of Li[N(SiMe3)2] resulted in the replacement of a Na+ by a Li+, giving the ionic complex [n 3:n2-{(C6H5CH2) 2C2B9H9}2ZrCl-(THF)] [Li(THF)4] (3). ClZr[N(SiMe3)2]3 was isolated from the reaction of 1 with excess Li-[N(SiMe3) 2]. An equimolar reaction between M(NEt2)4 and (C6H5CH2)2B9H 11 afforded the monocarboranyl complexes [n2-(C 6H5CH2)2C2B 9H9]M(NEt2)2(NHEt2) (M = Ti (5), Zr (6)). It is believed that the additional N(p π)→M(dπ) interactions stabilize this type of complex. Treatment of MCl4(THF)2 with 1 equiv of less bulky yet rigid [{o-C6H4(CH2) 2}C2B9H9]Na2-(THF) x generated a bent-metallocene type of complex, [{o-C 6H4(CH2)2}C2B 9H9]2M(THF)2 (M = Zr (7), Hf (8)). These metallacarboranes were all fully characterized by various spectroscopic techniques and elemental analyses. Molecular structures of 1 and 3-5 were confirmed by single-crystal X-ray analyses.
Reduction-induced cyclization and redox reactions of fully methylated titanocene dichlorides bearing pendant alkenyldimethylsilyl groups, [TiCl2{η5-C5Me4(SiMe2 R)}2] (R = vinyl and allyl)
Luke?ová, Lenka,?těpni?ka, Petr,Fejfarová, Karla,Gyepes, Róbert,Císa?ová, Ivana,Horá?ek, Michal,Kubi?ta, Ji?í,Mach, Karel
, p. 2639 - 2653 (2008/10/08)
The reactions initiated by the magnesium reduction of silicon-modified titanocene dichlorides [TiCl2(η5-C5Me4SiMe2 R)2] were reported. The features in subsequent oxidative addition reactions due to the presence of the silylene groups and different lengths of the silylalkenyl groups were showed. Pendant double bonds were used as reactive functionalities for modification of the parent bent metallocene structures.
