Reduction of nitriles with 2-propanol in presence of RhCl(PPh3)3 and RuCl2(PPh3)3

Conclusions The complexes RhCl(PPh₃)₃ and RuCl₂(PPh₃)₃ catalyze hydrogen transfer from 2-propanol to the C N bond of benzonitrile and capronitrile. The reduction rate of the aromatic nitrile is higher than that of the aliphatic nitrile.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1894–1895, August, 1976.     

The mechanism of the addition of tetrahaloalkanes to alkenes in the presence of RuCl2(PPh3)3

The addition of tetrahaloalkanes to alkenes in the presence of [RuCl₂(PPh₃)₃] has been examined in detail and it is suggested that it proceeds by a non-chain catalysed mechanism involving free radical intermediates.     

Substituent dependence of the reactions of [RuCl2(PPh3)3] with bulky aromatic thiols

2,4,6-trialkylbenzenethiols react with [RuCl2(PPh3)3] to give Ru products with the alkyl substituents forming M-C sigma bonds, carbene, carbene with a S alpha-heteroatom, agostic hydrogen interaction or a simple tetrahedral Ru(II) species, depending on the substituent.     

Amino alcohol additives for the fast living radical polymerization of methyl methacrylate with RuCl2(PPh3)3

A series of amino alcohols [e.g., R₂N (CH₂)_n OH (R = Me, Et, etc.; n = 2, 3, or 4)] were examined as additives for rate enhancement and finer reaction control in the living radical polymerization of methyl methacrylate with RuCl₂(PPh₃)₃. In general, these additives were more effective in acceleration than the corresponding amines as well as mixtures of an amine and a nonsubstituted alcohol, diamines, or diols. For example, 2-(diethylamino)ethanol significantly accelerated the polymerization (23 h, 91% at 60 °C) and gave polymers with narrower molecular weight distributions [weight-average molecular weight/number-average molecular weight (M_w/M_n) = 1.23], with respect to the system without the additive (550 h, 95%, M_w/M_n ∼ 2.0 at 80 °C; no polymerization at 60 °C). ¹H NMR analysis showed the interaction between the amino alcohols and RuCl₂(PPh₃)₃, which apparently formed a more active catalyst. Amino alcohols were also effective in Ru(Ind)Cl(PPh₃)₂-catalyzed systems (96% in 8 h at 80 °C). High-molecular-weight poly(methyl methacrylate) (M_n ∼ 1.1 × 10⁵) was synthesized with the RuCl₂(PPh₃)₃/2-(diethylamino)ethanol system, in which the polymerization reached 97% conversion in 4 h. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3597–3605, 2003     

The isomerization of n-butenes catalyzed by RhCl(PPh3)3-I. The isomerization of 2-butenes

In dichloromethane solution, cis- and trans-2-butene are catalytically isomerized by RhCl(PPh₃)₃. The slow reaction reaches the thermodynamic equilibrium of the three possible n-butenes. The isomerization shows a marked induction period. When pure cis-2-butene is isomerized, 1-butene temporarily reaches twice the equilibrium concentration. The kinetic data suggest that RhCl(PPh₃)₃ is not the catalytically active species. Dissociation of the original rhodium complex appears to be a requirement for the isomerization of the olefins.     

Effect of supercritical CO2 on bulk hydrogenation of nitrile butadiene rubber catalyzed by RhCl(PPh3)3

The effect of supercritical (SC) CO₂ on the bulk hydrogenation of NBR entrapped with the catalyst (RhCl(PPh₃)₃) was investigated under various reaction times, reaction temperatures, hydrogen pressures and loadings of the catalyst and the thicknesses of the polymer films. CO₂ helps in improving the transport behaviour of catalyst in polymer matrices, as well as helping to move catalyst into or out of the polymer. A method for the measurement of the dissolution extent or the apparent solubility of the Rh based catalyst in SC-CO₂ was developed. It is found that high temperatures and high SC-CO₂ densities would enhance the apparent solubility. Cosolvents, such as acetone, are also found to increase the apparent solubility. Details on the hydrogenation process are also presented.     

Synthesis and characterisation of [RuCl2(PPh3)2(C16H11NO)] complex

The reaction of [RuCl₂(PPh₃)₃] complex with 1-isoquinolyl phenyl ketone has been examined. A new ruthenium(II) complexes–[RuCl₂(PPh₃)₂(C₁₆H₁₁NO)] has been obtained and characterised by IR and UV-VIS measurements. Crystal structure of the complex has been determined. The electronic spectrum of the complex has been calculated by TDDFT method.     

Kinetics and mechanism of RuCl2PPh3)3-catalyzed oxidation of sulfides by N-methylmorpholine N-oxide

Oxidation of dibutylsulfide, diphenylsulfide, methylphenylsulfide and dibenzylsulfide to the corresponding sulfoxides by N-methylmorpholine N-oxide (NMO) catalyzed by RuCl₂(PPh₃)₃ in DMF solvent is reported. The reaction is first order in both catalyst and N-oxide. The order with respect to the substrate is variable, being zero at higher concentrations and fractional at lower concentrations. The order of reactivity observed for the substrates is as follows: dibutylsulfide ≈ dibenzylsulfide > methylphenylsulfide > diphenylsulfide. RuCl₂(PPh₃)₃ oxidizes olefins to form epoxides at a slower rate. The order of reactivity observed for the two types of substrates parallels their nucleophilicity (sulfides > alkenes).Spectral studies indicate 1:1 complex formation between RuCl₂(PPh₃)₃ and the sulfides. The active oxidant is the Ru(IV)oxo complex formed by the oxidation of Ru(II) by NMO.     

One-step synthesis of alkenyl ketone complexes from Cp*RhCl2(PPh3), alkyne and H2O in the presence of KPF6

The reaction of Cp*RhCl2(PPh3) 1 with 1-alkyne and H2O in the presence of KPF6 afforded the alkenyl ketone complex [Cp*Rh(PPh3)(CPh=CHCOCH2R)](PF6) [R = p-tolyl (3a), R = Ph (3b)], whereas Cp*IrCl2(PPh3) 2 or [(eta 6-C6Me6)RuCl2(PPh3) gave the corresponding [Cp*IrCl(CO)(PPh3)](PF6) 5a and [(eta 6-C6Me6)RuCl(CO)(PPh3)](PF6).     

Hydroformylation of Olefins by a Rhodium Single‐Atom Catalyst with Activity Comparable to RhCl(PPh3)3

Homogeneous catalysts generally possess superior catalytic performance compared to heterogeneous catalysts. However, the issue of catalyst separation and recycling severely limits their use in practical applications. Single‐atom catalysts have the advantages of both homogeneous catalysts, such as “isolated sites”, and heterogeneous catalysts, such as stability and reusability, and thus would be a promising alternative to traditional homogeneous catalysts. In the hydroformylation of olefins, single‐atom Rh catalysts supported on ZnO nanowires demonstrate similar efficiency (TON≈40000) compared to that of homogeneous Wilkinson's catalyst (TON≈19000). HAADF‐STEM and infrared CO chemisorption experiments identified isolated Rh atoms on the support. XPS and XANES spectra indicate that the electronic state of Rh is almost metallic. The catalysts are about one or two orders of magnitude more active than most reported heterogeneous catalysts and can be reused four times without an obvious decline in activity.     

Biphasic catalysis with RuCl2(DMSO)(TPPMS)3

A mononuclear RuCl₂(DMSO)(TPPMS)₃ complex (1) (TPPMS = triphenylphosphine monosulfonate) has been synthesized. Spectroscopic analysis by i.r., u.v.–vis., ¹H-, ¹³C-, ³¹P-n.m.r., cyclic voltammetry, m.s. analysis and MO calculations were in agreement with a possible octahedral structure. Biphasic (H₂O/PhMe) catalytic studies have shown good olefin hydrogenation activity by the complex at moderate temperature and pressure.     

Organometallic macrocycle chemistry: I. The reactions of [RuCl2(PPh3)3]with 1,4,7-trithiacyclononane and 1,4,8,11-tetrathiacyclotetradecane

The reactions of [RuCl₂(PPh₃)₃] with the thiacrown ethers 1,4,7-trithiacyclononane (9-S3) and 1,4,8,11-tetrathiacyclotetradecane (14-S4) pr