Titanium and zirconium neopentyl chloro complexes, MNpxCl4−x (x = 1−4)

Abstract

Abstract The comproportionation reaction between the titanium and zirconium homoleptic neopentyl complexes, TiNp 4 and ZrNp 4 (Np = 2,2′-dimethylpropyl; CH 2 CMe 3 ) and the metal tetrachlorides, TiCl 4 and ZrCl 4 provides a facile route to all of the titanium and zirconium neopentyl chloro complexes, MNp x Cl 4− x ( x = 1,2,3). All the complexes described are moisture-sensitive, and in the case of the titanium complexes, light-sensitive also. The stability of the complexes at room temperature has also been estimated. The neopentyl chloro complexes, and the isotopically labelled species (where (Np- d ) = CH(D)CMe 3 ), have been spectroscopically characterised, the 1 H NMR resonance of the CH 2 protons displays an increasing shift to high frequency in the series MNp 4 , MNp 3 Cl, MNp 2 Cl 2 , MNpCl 3 . A modified synthesis of Me 3 CCHDCI from Me 3 CCHDOH is reported.