68193-40-8Relevant articles and documents
An NMR study on the reaction of substituted dimethyl zirconocenes with dimethylanilinium borate
Rocchigiani, Luca,Bellachioma, Gianfranco,Zuccaccia, Cristiano,MacChioni, Alceo
, p. 32 - 40 (2012/09/11)
The reaction of a series of dimethyl zirconocenes [Me2Si(Cp) 2ZrMe2, 1; Cpt-bu2ZrMe2, 2; Cpn-bu2ZrMe2, 3; Ind2ZrMe 2, 4; CpMe42ZrMe2, 5; Cp 2ZrMe2, 6] with [HNMe2Ph][B(C6F 5)4] was investigated by means of NMR spectroscopy. It was found that protonolysis of a Zr-Me group occurred generating a coordinative vacancy at the metal center and methane. Cations coming from 1-4 dimethyl precursors bound NMe2Ph, liberated from the protonation process, and formed zirconaaziridinium ion pairs {[Me2Si(Cp)2Zr(η 2-CH2NMePh)][B(C6F5)4], 7; [Cpt-bu2Zr(η2-CH2NMePh)] [B(C6F5)4], 8; [Cpn-bu 2Zr(η2-CH2NMePh)][B(C6F 5)4], 9; [Ind2Zr(η2-CH 2NMePh)][B(C6F5)4], 10}, reasonably as a consequence of CH activation of one Me group of coordinated NMe 2Ph and methane elimination. The intramolecular/interionic structures and dynamics of 7-10 ion pairs were investigated by 1H, 13C and 19F 1D-and 2D-NMR techniques. The reactions of 7 and 10 ion pairs with 2-methyl-1-heptene afforded stable diastereoisomeric ion pairs bearing a five-member azametallacycle.
Stereochemical nonrigidity in metallocenium ions
Siedle, A. R.,Newmark, R. A.
, p. 119 - 126 (2007/10/02)
Dynamic NMr spectrscopy of the MeB(C6F5)3- salts of a series of ring-substituted zirconium- and hafnium-containing metallocenium ions, exemplified by (RCp)2ZrCH3+, reveals two exchange processes.One, having the lower free energy of activation, involves shift of the CH3 group from one lateral equatorial orbital to the other.The second results from exchange between the metal-CH3 and B-CH3 groups.Effects of structural variations on exchange barriers are discussed and related to metallocenium ion-catalyzed olefin polymerization.Keywords: Metallocenium ions; Stereochemical nonrigidity; Zirconium; Hafnium
SYNTHESE ET REACTIVITE DE NOUVEAUX DIHYDRUROZIRCONOCENES ET-HAFNOCENES SUBSTITUES ACHIRAUX ET CHIRAUX
Couturier, S.,Tainturier, G.,Gautheron, B.
, p. 291 - 306 (2007/10/02)
Hydrogenolysis of (M(CH3)2) (M=Zr, Hf) bonds gives new racemic and optically active substituted zirconocene and hafnocene dihydrides A: (RCp)2MH2 (M=Zr, Hf; R=Me, Me2CH, Me3C, PhCH2) and B: (R*Cp)2MH2 (M=Zr, Hf; R*=MeCHEtCH2, PhCHEtCH2), R*CpCpHfH2 (R*=PhCHCH3).Substitution of hydridic hydrogens by halogens, mobile hydrogen compounds, addition with unsaturated derivatives are studied.The A and B type complexes are good catalysts in hydrogenation of alkenes; the B type complexes give only poor asymmetric induction in catalytic reduction of prochiral alkenes.