1391997-14-0Relevant 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.