Ruthenium complexes of eta1 and eta5 vinyl phosphines

[(eta5-MeC5H4)Ru(eta 3-DPVP)(eta1-DPVP)]PF6 (6) was obtained by thermolysis under vacuum of [(eta5-MeC 5H4)Ru(CH3CN)(DPVP)2]PF6 (4) for several days at elevated temperature. It contains the eta 3-phosphaallyl ligand bound to ruthenium in the exo orientation. Compound 4 reacts with Me3SiC≡CH in CH2Cl2/MeOH solution to give methoxymethylcarbene complex [(eta5-MeC5H4)(DPVP)2 Ru=C(OCH3)(CH3)]PF6 (7). Reaction of 4 with PhC≡CH and adventious of H2O produces the carbonyl complex [(eta5-MeC5H 4)Ru(DPVP)2(CO)]PF6 (8).;[(eta5-C5H5)Ru(eta3-DCVP)(eta 1-DCVP)]PF6 (11) and [(eta5-MeC 5H4)Ru(eta3-DCVP)(eta1-DCVP)]PF 6 (12) were formed by addition of DCVP to [(eta 5-RC5H4)Ru(CH3CN)3]PF 6 (R = H, CH3) and by stirring overnight at room temperature. Compound 11 has the exo geometry and compound 12 was obtained as a 7:1 mixture of exo and endo isomers. They react with PhC≡CH, Me3SiC≡CH (12) and CO, PhNC (11 and 12) at the metal center displacing the coordinated vinyl moiety. The enhanced stability of phosphaallyl complexes 11 and 12 is a result of better donor ability of DCVP than DPVP and the greater steric bulk of cyclohexyl than phenyl group.;CH3CN could not be displaced by the vinyl group of DPVP and DCVP in [(eta5-MeC5H4)Ru(CO)(CH 3CN)(DPVP)]PF6 (24), [(eta5-C 5Me5)Ru-(CO)(CH3CN)(DPVP)]PF6 ( 25) and [(eta5-MeC5H4)Ru(CO)(CH 3CN)(DCVP)]PF6 (27). We wondered if other ligands would displace the CH3CN from these complexes or if it were substitutionaily inert. Two compounds 24 and 25 react with 3,4-dimethyl-1-phenylphosphole (DMPP) and undergo [4+2] Diels-Alder cycloaddition reaction with only modest diastereoselectivity.;Metal catalyzed hydration of alkynes is an important route to carbonyl compounds. We have conducted tests with [(eta5-MeC5 H4)Ru(CO)(CH3CN)(DPVP)]PF6 ( 24), [(eta5-C5Me5)Ru(CO)(CH 3CN)(DPVP)PF6 (25), [(eta5-C 5H5)Ru(eta3-DCVP)(eta1-DCVP)]PF 6 (11), [(eta5-MeC5H4 )Ru(eta3-DCVP)(eta1-DCVP)]PF 6 (12) and [(eta5-MeC5H 4)Ru(eta3-DPVP)(eta1-DPVP)]PF 6 (6) as catalysts for the hydration of phenylacetylene. Neither acetophenone nor phenylacetaldehyde was detected in any of these tests. Instead, phenylacetylene dimers and dimers were identified.