Phosphaallyl complexes of Ru(II) derived from dicyclohexylvinylphosphine (DCVP)

摘要

The complexes [(eta(5)-RC5H4) Ru(CH3CN)(3)] PF6 (R = H, CH3) react with DCVP ( DCVP = Cy2PCH = CH2) at room temperature to produce the phosphaallyl complexes [(eta(5)- C5H5) Ru(eta(1)-DCVP)(eta(3)-DCVP)] PF6 ( 1) and [(eta(5)-MeC5H4) Ru(eta(1)-DCVP)(eta(3)-DCVP)] PF6 (2). Both compounds react with a variety of two-electron donor ligands displacing the coordinated vinyl moiety. In contrast, we failed to prepare the phosphaallyl complexes [(eta(5)-C5Me5) Ru(eta(1)-DCVP) (eta(3)-DCVP)] PF6, [(eta(5)-MeC5H4) Ru(CO)(eta(3)-DCVP)] PF6 and [(eta(5)-C5Me5) Ru(CO)(eta(3)-DPVP)] PF6 (DPVP = Ph2PCH= CH2). The compounds [(eta(5)-MeC5H4) Ru(CO)(CH3CN)(DPVP)] PF6 and [(eta(5)-C5Me5) Ru(CO)(CH3CN)(DPVP)] PF6 (12) react with DMPP (3,4-dimethyl-1-phenylphosphole) to undergo [4 + 2] Diels - Alder cycloaddition reactions at elevated temperature. Attempts at ruthenium catalyzed hydration of phenylacetylene produced neither acetophenone nor phenylacetaldehyde but rather dimers and trimers of phenylacetylene. The structures of the complexes described herein have been deduced from elemental analyses, infrared spectroscopy, H-1, C-13{H-1}, P-31{H-1} NMR spectroscopy and in several cases by X-ray crystallography.