Activation of η⁵-Cyclopentadienyl Ligands toward Nucleophilic Attack through η⁵ → η³ Ring Slippage. Kinetics, Thermodynamics, and NMR Spectroscopy

Abstract

The kinetics of the reactions of the complexes [Ru(η5-C5H5)(η4-C5H4O)(L)]CF3SO3 (L = CH3CN, pyridine, thiourea) with PMe3 have been studied in acetone. The novel reaction products [Ru(η3-C5H5)(η4-C5H4O)(PMe3)(L)]CF3SO3 formed are fluxional in solution due to an intramolecular enantiomeric equilibrium likely proceeding through a five-coordinate η1-C5H5 intermediate.