122116-95-4Relevant academic research and scientific papers
Five- and Six-Coordinate Vinyl-Ruthenium and -Osmium Complexes by Alkyne Insertion from Hydrido-Metal Precursors
Werner, Helmut,Meyer, Uwe,Peters, Karl,Schnering, Hans Georg von
, p. 2097 - 2108 (2007/10/02)
The carbonyl-hydrido complexes MHCl(CO)2 (3: M = Ru; 4: M = Os) react with alkynes RCCH (R = H, Me, Ph) by insertion to give the five-coordinate vinyl-metal compounds M(E-CH=CHR)Cl(CO)2 (5-10) in high yield.Using MHCl(CO)(PiPr3)2 (11, 12) and RuHCl(CO)(PPh3)3 (15) as starting materials, the complexes M(E-CH=CHMe)Cl(CO)(PiPr3)2 (13, 14) and Ru(E-CH=CHR)Cl(CO)(PPh3)2 (16: R = Ph; 17: R = H) are similarly prepared.The reactions of 3, 4, and 12 with HCCCO2Me also lead to the formation of vinyl-metal compounds in which the CO2Me group is either bound to the α or the β carbon atom of the vinyl ligand.The X-ray crystal structure of (18) has been determined.In solution, Os(E-CH=CHCO2Me)Cl(CO)(PiPr3)2 (22) rearranges quantitatively to form the Z isomer 24 in which the vinyl group behaves as a chelating ligand.The hydrido complexes 3, 4, and the vinyl-metal compounds 5-10, 13, 16, and 31 react with L (CO, CNMe, CNCH2Ph and PMe3) to give the corresponding octahedral ruthenium and osmium derivatives 25-30 and 32-39 in almost quantitative yields.The ionic complex PF6 (41) has also been prepared. - Key Words: Alkyne insertion / Chelating vinyl ligands / Vinyl metal complexes
