910804-35-2Relevant academic research and scientific papers
Models for solvation of zirconocene cations: Synthesis, reactivity, and computational studies of cationic zirconocene benzyl compounds
Sassmannshausen, Joerg,Track, Anna,Stelzer, Franz
, p. 4427 - 4432 (2006)
The reactions of the zirconocene compounds [(η5-C 5H5)2-Zr(CH2C6H 4R)2] (R = F (1), CMe3 (2), Me (3)) with either B(C6F5)3 or the trityl salt [Ph 3C]+[B(C6F5)4] - in CD2Cl2 were monitored by NMR spectroscopy. In all cases, the cationic compound [(η5-C5H 5)2-Zr(η2-CH2C6H 4R)]+ was obtained, irrespective of the activator used (B(C6F5)3 or the trityl salt). Whereas NMR studies suggest a η2-coordination of the benzyl ligand to the cationic zirconium metal, detailed DFT studies revealed that in CD 2Cl2 this is only the case if one solvent molecule is coordinated via the lone pair of one chlorine to the metal. Without this coordination, a η3-coordination is more likely to occur. Computed NMR shifts at the B3LYP/IGLO II level corroborate this observation, which is in concert with a detailed NBO analysis of the cationic zirconocene compounds.
