Synthesis, Structure, and Reactivity of Dicationic Bimetallic Tetrabenzyldihafnium Complexes Bearing a Chelating (2-Hydroxyethyl)amido Ligand

Abstract

We prepared the bimetallic hafnium complex 1 by reaction of Hf(CH 2 Ph) 4 with the alcohol-imine proligand L via deprotonation and subsequent benzyl migration from the hafnium atom to the imine moiety of L. The complex 1 was obtained as a diastereomeric mixture of 1a (SR, heterochiral) and 1b (RR and SS, homochiral); the SR isomer 1a was readily isolated by simply washing with toluene. Treatment of 1a with [Ph 3 C][B(C 6 F 5 ) 4 ] in C 6 H 5 Cl afforded the dicationic complex 2a, which was characterized by spectroscopic data and an X-ray diffraction study, revealing the η 6 coordination of the phenyl group bound to the chelating ligand to the cationic hafnium center. Complex 2a showed catalytic activity for 1-hexene oligomerization at 100 °C in combination with 2 equiv of [Ph 3 C][B(C 6 F 5 ) 4 ], while 4,4′dimethoxydiphenylacetylene reacted with 2a to quantitatively afford alkene 3 at room temperature after hydrolysis. The addition of PMe 2 Ph and pyridine to 2a dissociated the η 6 -arene coordination of the ligand to give the corresponding adducts 5a and 6a, whose structures were fully characterized by X-ray diffraction analysis. Article pubs.acs.org/Organometallics