307982-37-2Relevant academic research and scientific papers
Formation of Di- And Tricarbonylruthenium(O) Species from [RuH2(CO)(PPh3)3] via Decarbonylation of Methyl Benzoates: X-Ray Crystal Structures of [Ru(CO)2(PPh3)3] and [Ru(O2)(CO)2(PPh3)2]
Hiraki, Katsuma,Kira, Shu-Ichi,Kawano, Hiroyuki
, p. 1583 - 1592 (1997)
Dihydridoruthenium(II) complex [RuH2(CO)(PPh3)3] (1) reacts with methyl benzoate in the presence of an olefin at 110 °C to afford some dicarbonylruthenium(O) species [Ru(CO)2(PPh3)3] (2) and Ru(CO)2(PPh3)2L (L= the olefin or the ester). A tricarbonylruthenium(O) complex [Ru(CO)3(PPh3)2] (3) is formed at higher reaction temperature. The experiment using 13C-enriched methyl benzoate reveals that the second and the third carbonyl ligands are mainly derived by subtraction of the carbonyl group from the ester. When the reaction is carried out in the presence of triethoxyvinylsilane, a part of the second and the third carbonyl groups is derived from the ethoxy group of the silane, because 1 reacts with the silane at 110 °C in the absence of the ester to afford 2 and 3. The formation ratio of 2 and 3 is affected by the type of olefins used; selective formation of 2 and 3 is achieved when triethoxyvinylsilane is used, whereas allylbenzene or cyclooctene affords merely a mixture of the di- and tricarbonyl species. The reaction mixture containing 2 and Ru(CO)2(PPh3)2L is exposed to air to give a peroxo complex [Ru(η2-O2)(CO)2 (PPh3)2] (4) smoothly. The molecular structures of 2 and 4 are determined by the single crystal X-ray diffraction method. The complex 2 has a distorted trigonal bipyramidal coordination geometry with two equatorial CO ligands, whereas the complex 4 has a distorted octahedral structure.
Room-temperature regioselective c-H/olefin coupling of aromatic ketones using an activated ruthenium catalyst with a carbonyl ligand and structural elucidation of key intermediates
Kakiuchi, Fumitoshi,Kochi, Takuya,Mizushima, Eiichiro,Murai, Shinji
, p. 17741 - 17750 (2011/03/16)
Mechanistic studies of the ruthenium-catalyzed reaction of aromatic ketones with olefins are presented. Treatment of the original catalyst, RuH 2(CO)(PPh3)3, with trimethylvinylsilane at 90 °C for 1-1.5 h afforded an activ
An NMR study on the ruthenium complex-catalyzed C-H/olefin coupling reaction
Hiraki, Katsuma,Ishimoto, Takayuki,Kawano, Hiroyuki
, p. 2099 - 2108 (2007/10/03)
A dihydridoruthenium(II) complex, [RuH2(CO)(PPh3)3], reacts with styrene to give two species: A bis(styrene)-ruthenium(0) complex, [Ru(CO)(CH2=CHPh)2(PPh3)2], and a cyclometallated hydridoruthenium(II) one, [Ru(C6H4PPh2)-H(CO)(PPh3)2]. The complex [RuH2(CO)(PPh3)3] reacts with isoprene to give a piano-stool type ruthenium(0) complex [Ru(η4-CH2CMeCH=CH2)(CO)(PPh3)2]. In reactions among [RuH2(CO)(PPh3)3], styrene, and 3'-(trifluoromethyl)acetophenone, three cyclometallated hydridoruthenium(II) complexes: P,P'-cis-C,H-cis-, P,P'-trans-C,H-trans-, and P,P'-trans-C,H-cis-[Ru{C6H3(CF3)C(=O)Me}H(CO)(PPh3)2] are detected by NMR spectroscopy. The 1H NMR spectra of the reaction mixture exhibit the catalytic formation of 2'-(2-phenylethyl)- and 2'-(1-phenylethyl)-5'-(trifluoromethyl)acetophenones. On the basis of these findings, a mechanism for the C-H/olefin coupling reaction is discussed. The first of the three complexes is assigned to an active intermediate in the catalytic coupling reaction, whereas the other two are assigned as quasi-stable ruthenium(II) complexes which are in equilibrium with active species.
COMBINED DECARBOXYLATION OF THE FORMATO LIGAND AND REDUCTIVE ELIMINATION OF HYDRIDO AND ARYL GROUPS IN THE SYNTHESIS OF RUTHENIUM(0) COMPLEXES. METHYLATION OF RUTHENIUM(0) WITH FORMALDEHYDE
Roper, W.R.,Wright, L.J.
, p. C5 - C8 (2007/10/02)
The formato ligand is readily introduced into the 5-coordinate complexes MRCl(CO)(PPh3)2 (M = Ru or Os, R = o-tolyl) giving 6-coordinate MR(η2-O2CH)(CO)(PPh3)2.In the presence of excess PPh3 thermal decarboxylation of the osmium complex leads to the stable aryl, hydride, OsRH(CO)(PPh3)3.A similar reaction with RuR(η2-O2CH)(CO)(PPh3)2 is accompanied by reductive elimination of RH and formation of Ru(CO)(PPh3)3 which as a solid is ortho-metallated, i.e. exists as .Decarboxylation and reductive elimination in the presence of bis(diphenylphosphino)ethane (dppe) give the zerovalent Ru(CO)(dppe)2. Ru(CO)(PPh3)3 undergoes a most unusual reaction with formaldehyde forming Ru(CH3)(η2-O2CH)(CO)(PPh3)2.
