CYCLOPENTADIENYL-RUTHENIUM AND -OSMIUM CHEMISTRY. XXV. CONVERSION OF ALKOXYCARBENE COMPLEXES TO VINYL ETHER DERIVATIVES: X-RAY STRUCTURE OF Ru(C(OPrI)=CHPh)(CO)(PPh3)(η-C5H5)

Article abstract of DOI:10.1016/0022-328X(85)87197-7

Several cationic alkoxy(alkyl)carbene complexes containing the Ru(L)(PPh3))η-C5H5) (L=CO or PPh3) moiety have been deprotonated with NaOMe to the corresponding vinyl ether derivatives.The reaction is reversed by addition of PF6.Many of the vinyl ether complexes were obtained as mixtures of E and Z isomers; the X-ray structure of Ru(C(OPrⁱ)=CHPh)(CO)(η-C5H5) shows that it is obtained only as the E isomer, and that unit cell contains equal numbers of the two enantiomers.Ru(C(OPrⁱ)=CHPh)(CO)(PPh3)(η-C5H5) is monoclinic, space group P2₁/c, with 10.337(5), b 15.161(4), c 18.714(5) Angstroem, β 90.83(3) deg, and Z=4; 2240 reflections 2.5?*I(> were refined to R=0.0388, R_w=0.0436.Important distances: Ru-C(vinyl) 2.103(6), Ru-CO 1.832(7), Ru-P 2.298(2), C=C(vinyl) 1.335(8), C-OMe 1.381(7) Angstroem.Addition of NaOMe to the product of the reaction between RuCl(PPh3)2(η-C5H5) and HC<*>CC(O)Me in MeOH afforded a mixture of Ru(C<*>CC(O)Me)(PPh3)2(η-C5H5) and Ru(C(OMe)=CHC(O)Me)*PPh3)2(η-C5H5).The latter losses PPh3 on standing in solution ar ambient temepratures, forming the chelate complex cyclo-Ru(C(OMe)=CHC(O)Me(PPh3)(η-C5H5).The similar conversion of Ru(C(OMe)=CHC(O)Me)(PPh3)2(η-C5H5) to the corresponding chelate complex required heating at 65 def C for 75 minutes.