122115-88-2Relevant academic research and scientific papers
Kinetic and Mechanistic Investigation of the Sequential Hydrogenation of Phenylacetylene Catalyzed by OsHCl(CO)(PR3)2
Andriollo, Antida,Esteruelas, Miguel A.,Meyer, Uwe,Oro, Luis A.,Sanchez-Delgado, Roberto A.,et al.
, p. 7431 - 7437 (1989)
The reactivities of the hydrido carbonyl complexes OsHCl(CO)(PR3)2 toward hydrogen, alkynes, and oxygen have been studied.The solutions of 1 and 2 are rapidly decolorized upon contact with H2 under ambient conditions; the decolorized solution of 2 shows in benzene-d6 a (1)H NMR spectrum that is consistent with the formation of the dihydrogen compound OsHCl(η2-H2)(CO)(P-i-Pr3)2 (3).The reactivity of 1 and 2 toward alkynes depends on the type of alkyne used.The title complexes react with acetylene, propyne, and phenylacetylene by insertion to give the five-coordinate vinylosmium compounds Os(CH=CHR)Cl(CO)(PR3)2 (7 and 8); the same starting materials in the presence of and are completely inert.Treatment of 2 with leads to the compound ; the trans- and cis-alkyne hydrido intermediates have been observed.The hydridoosmium(II) complexes 1 and 2 also react with O2 to form the dioxygen adducts OsHCl(η2-O2)(CO)(PR3)2 (11 and 12).The complexes 1 and 2 catalyze the sequential hydrogenation of phenylacetylene in 2-propanol solution at 60 degC.Selectivities close to 100percent are achieved for the hydrogenation of the alkyne to the alkene.The kinetic investigation of this reaction provides evidence that indicates that the formation of styryl derivatives is the step that determines the selectivity for the hydrogenation to the alkene.
Synthesis and Reactions of Hydrido(oxime), Hydrido(oximato) and Alkenyl(oximato) Complexes of Ruthenium and Osmium
Meyer, Uwe,Werner, Helmut
, p. 697 - 702 (2007/10/02)
The carbonyl(hydrido) complexes MHCl(CO)2 (4: M= Ru; 5: M= Os) react with aldoximes and ketoximes to give the octahedral hydrido(oxime)ruthenium and -osmium compounds MHCl(CO)2 (8-13) in high yields.Using MHCl(CO)(PiPr3)2 (6,7) as starting materials, the complexes MHCl(CO)(PiPr3)2 (14-16) are obtained.Reactions of 9 (M= Os; R= R'= CH3) illustrate that the oxime ligand in the hydrido(oxime) compounds is easily displaced by Lewis bases.Either from 4, 5 and Na in methanol or from 8-13 and NaH in THF the hydrido(oximato) complexes 20-25 in which the oximato ligand is coordinated via N and O, are formed almost quantitatively.CO opens the three-membered ring by cleavage of the M-N bond.Analogously, the alkenyl(oximato) compounds 28-30 are obtained from MCl(CO)2 (18: M= Os; 27: M= Ru) with Na.
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
