Synthesis, characterization, and reactivity of the first hafnium alkyl complex stabilized by amidate ligands

A photo and thermally stable bis(amidate)-dibenzyl complex of Hf ([(DMP)(NO)(Ph)](2)Hf(CH2Ph)(2)(THF) (2a) was formed as a monosolvated THF adduct in near quantitative yield from Hf(CH2Ph)(4) and N-2,6-dimethylphenyl(phenyl)amide (1). Isomerization between the THF-bound product and the THF-free product can be observed visually by the conversion from a red-orange product at low temperatures to a pale yellow product at high temperatures. Solid-state crystallographic characterization of the orange product confirmed its constitution as a monosolvated species. Kinetic parameters for the exchange of the THF moiety were determined from variable-temperature NMR experiments. The product of the hydrolysis of the Hf dibenzyl species by water was characterized by X-ray crystallography, and was found to be a rare tetrametallic Hf oxo cluster species (3).