ChemInform Abstract: Dynamic Binuclear Enediolato- and Catecholato-Zirconocene Complexes Relevant to the Structural Problem Associated with Sharpless Oxidation Catalysts.

Abstract

Dimethylzirconocene complexes [ZrMe2(C5H4R)2](R = H or CH3) were treated with catechol to give the (catecholato)zirconocene complexes. Low-temperature NMR spectra indicated dimeric metallatricyclic structures for these complexes and the corresponding (ethene-1,2-diolato)- and (but-2-ene-2,3-diolato)-zirconocenes. Dynamic temperature-dependent NMR spectroscopy revealed that all these complexes underwent a thermally induced degenerate rearrangement process, similar to the reorganization reaction of some Sharpless catalyst precursors, with Gibbs activation energies close to 50 kJ mol–1. A labelling experiment showed the intramolecular nature of this automerization. (4-tert-Butylcatecholato)zirconocene formed two diastereoisomeric dimers which did not interconvert on the NMR time-scale (ΔG‡inter >90 kJ mol–1) although the intramolecular rearrangement was observed [ΔG‡intra(241 K)= 52 ± 2 kJ mol–1]. The intermolecular equilibration process probably proceeding via monomeric (catecholato)zirconocene was monitored in the case of the bulky (4-tert-butyl-catecholato)bis(tert-butylcyclopentadienyl)zirconium system by dynamic NMR spectroscopy at high temperature [ΔG‡inter(364 K)= 78 ± 5 kJ mol–1].