Synthesis, structure and molecular dynamics of η2-iminoacyl compounds[Cp(ArO)Zr(η2-ButNCCH2Ph)(CH2Ph)] and [Cp(ArO)Zr(η2-ButNCCH2Ph)2]

The reaction of the substrate [CpZr(CH2Ph)(3)] with the ligands 2,3,5,6-tetraphenyl-1,2-phenyl-4,6-di-tert-butyl-2 or 2-(1-naphthyl)-4,6-di-tert-butyl-phenol 3 leads to the corresponding compounds [Cp(ArO)Zr(CH2Ph)(2)] 4-6. Solution studies show that naphthyl rotation is slow on the NMR timescale at ambient temperatures within 6 leading to nonequivalent benzyl groups with diastereotopic methylene protons. The solid-state structure of 5 shows both benzyl ligands to be eta(1)-bound. Compounds 4-6 react with tert-butylisocyanide in hydrocarbon solvents to initially produce the mono( iminoacyl) derivatives [Cp(ArO)Zr(eta(2)-(BuNCCH2Ph)-N-t)(CH2Ph)] 7-9 followed by the bis(iminoacyl) products [Cp(ArO) Zr(eta(2)-(BuNCCH2Ph)-N-t)(2)] 10-12. In the solution C-13 NMR spectra of the iminoacyl derivatives the Zr-CN carbon atom resonates at delta 242-244 ppm (7-9) and delta229-234 ppm (10-12) consistent with the eta(2)-C, N binding. This was confirmed in the solid state by X-ray diffraction studies of 8, 11 and 12. At ambient temperatures only one set of iminoacyl resonances are observed for 10 and 11, indicating that both iminoacyl rotation and aryloxide rotation are facile. At lower temperatures the iminoacyl ligands in 11 become non-equivalent in the 1 H NMR spectrum consistent with restricted rotation about the Zr-O-Ar bond. The iminoacyl ligands in the 2-(1-naphthyl) derivative 12 are non-equivalent in solution NMR spectra from -75 to +85 degreesC. The solution fluxionality of these molecules as determined by NMR studies is discussed in detail.