1282-31-1Relevant articles and documents
Stereochemical course of π-face coordination to isodicyclopentadiene during formation of mixed titanocene and zirconocene dichloride complexes
Paquette, Leo A.,Moriarty, Kevin J.,Meunier, Philippe,Gautheron, Bernard,Sornay, Carole,Rogers, Robin D.,Rheingold, Arnold L.
, p. 2159 - 2167 (2008/10/08)
Reaction of the isodicyclopentadienide anion with RCpTiCl3 (R = H, CH3, t-Bu) and Cp″TiCl3 in tetrahydrofuran solution at -78°C is shown to proceed stereoselectively with formation of endo titanocene dichloride complexes. When the same reactions are performed at 20°C up to the reflux temperature of the solvent, the stereoisomeric exo complexes are cleanly formed instead. Control experiments have not led to the interconversion of these isomer pairs. Comparable reaction of isodiCpLi with CpZrCl3 and Cp″ZrCl3 in boiling tetrahydrofuran also delivered only exo complexes. The structural parameters of several products, as defined by X-ray crystallographic analysis, are discussed. The endo complexes appear to be more sterically constrained than the exo isomers. Their formation at low temperatures is thought to be kinetically controlled and to stem from electronic features imparted to the Cp anion portion of the isodicyclopentadienyl ligand by its fused norbornyl framework.
Effects of methyl substituents at the cyclopentadienyl ligand on the properties of C2H5TiCl3 and C5H5TiAl2CL8-x(C2H5)x (x = 0-4) complexes
Mach, Karel,Varga, Vojtech,Antropiusova, Helena,Polacek, Jindrich
, p. 205 - 216 (2007/10/02)
The methyl substituents in the series of pTiCl3 compounds (p = Cp, MeCp, Me3Cp, Me4Cp, Me5Cp and EtMe4Cp) shift the position of their CT absorption band from λ = 384 nm to max. 438 nm and decrease the rate of reduction of pTiCl3 by ethylaluminium
