cas 55102-19-7, CHLOROHYDRIDOTRIS(TRIPHENYLPHOSPHINE)RUTHENIUM (II)

Articles about 55102-19-7Total 16 be found

Article title
Article abstract
Author
Journal number and time
Download

Olefins isomerization by hydride-complexes of ruthenium
Several complexes containing the Ru-H bond were synthesized according to previous reports: RuH(NO)(PPh3)3(I) (1), RuHCl(PPh3)3(s)(II) (2), RuHCl(CO)(PPh3)3(II) (3), RuH(CH3COO)(P
Yue, Chuan Jun,Liu, Ying,He, Ren
p. 17 - 23
(2006)
Read Online

Kinetics and mechanisms of homogeneous catalytic reactions. Part 16. Regioselective hydrogenation of quinoline catalyzed by dichlorotris(triphenylphosphine)ruthenium(II)
The complex RuCl2(PPh3)3 (1) showed to be an efficient and regioselective precatalyst for the hydrogenation of quinoline (Q) to 1,2,3,4-tetrahydroquinoline (THQ) at P = 5.0–6.5 at m and T = 140?167 °C. This reaction showed to be first order on catalyst concentration and fractional order on dissolved hydrogen concentration (1.84). However, different to other Ru, Os, Rh and Ir precatalysts, the reaction showed an inverse fractional order on Q concentration (-0.44). The rate law may be written as: r = {KoK1k2/(Ko + [Q]+ KoK1[H2])}[Ru][H2]2. Coordination chemistry and theoretical DFT studies allowed us to propose a detailed catalytic cycle for this reaction. Under the hydrogenation conditions, the ruthenium precursor 1 is totally transformed to RuCl2(κN-Q)2(PPh3)2 (3) and subsequently to RuHCl(κN-Q)2(PPh3)2 (4) by heterolytic addition of H2. Complex 4 reversibly dissociates a Q ligand to generate RuHCl(κN-Q)(PPh3)2, which was proposed as the catalytically active species (CAS) entering to the catalytic cycle. The reversible addition of hydrogen yields a species containing a κN-1,2-dihydroquinoline (κN-DHQ) ligand (possibly through the coordination of hydrogen, migration of hydride to the N atom of Q ligand and posterior DHQ reductive elimination); this species suffers a change of coordination mode from κN- to an olefin-like η2-DHQ. Posteriorly, the addition of a second molecule of H2, considered the rate-determining step, generates a THQ species (probably through migration of hydride to C3 of DHQ ligand followed by the heterolytic addition of hydrogen). The cycle is completed by the substitution of the THQ ligand by a new Q molecule, therefore regenerating the CAS.
Arrieta, Federico,Baricelli, Pablo J.,Fernández, Dángelo,Molina, Karely,Rosales, Merlín
(2020)
Read Online

Homogeneous catalytic hydrogenation. 4. Regioselective reduction of polynuclear heteroaromatic compounds catalyzed by hydridochlorotris(triphenylphosphine)ruthenium(II)
The selective reduction of polynuclear heteroaromatic nitrogen compounds such as quinoline, 1, 5,6-benzoquinoline, 2, 7,8-benzoquinoline, 3, acridine, 4, phenanthridine, 5, and indole, 7, and in one case the sulfur heterocycle benzothiophene, 6, with hydridochlorotris(triphenylphosphine)ruthenium(II) as catalyst, under rather mild hydrogenation conditions, provided in each case the corresponding saturated nitrogen-or sulfur-containing ring compound with reasonable conversion rates and total yields. In addition, it was found that several compounds would inhibit the reduction of 1, to 1,2,3,4-tetrahydroquinoline, 8, including 8 itself, as well as 2, 7, 9 (2-methylpyridine), 10 (3-methylpyridine), and 11 (carbazole). Compounds 3 and 6 did not inhibit the rate of reduction. These inhibitions are seen as effects of competition for binding to the catalyst metal center, this competitive binding being affected by steric constraints and electronic effects such as basicity of the substrates. The substitution of deuterium gas for hydrogen gas in the reduction of 1 provided information on the reversibility of the hydrogenation step and implies a cyclometalation reaction is occurring leading to exchange of the 8-position of the product. Additional deuterium experiments starting with 8 instead of 1 indicate that the catalyst can partially dehydrogenate 8 to form an imine intermediate leading to deuterium exchange at the 2-position.
Fish, Richard H.,Tan, John L.,Thormodsen, Arne D.
p. 1743 - 1747
(1985)
Read Online

Coordination, agostic stabilization, and C-H bond activation of N-alkyl heterocyclic carbenes by coordinatively unsaturated ruthenium hydride chloride complexes
The products formed upon reaction of Ru(PPh3)3HCl and [Ru(PiPr3)2HCl]2 with the N-heterocyclic carbenes l,3-diisopropyl-4,5-dimethylimidazol-2-ylidene (I iPr2Me2,1) and 1,3-dieth
Burling, Suzanne,Mas-Marza, Elena,Valpuesta, Jose E. V.,Mahon, Mary F.,Whittlesey, Michael K.
p. 6676 - 6686
(2009)
Read Online

A tertiary phosphine that is too bulky: preparation of catalytically less active carbene and vinylidene ruthenium(II) complexes
Tricyclooctylphosphine PCoc3 (1), which has been prepared from PCl3 and cyclooctyl Grignard reagent, reacts under an atmosphere of H2 with the dimer [RuCl2(η3:η3 -C10H16/su
Stüer, Wolfram,Wolf, Justin,Werner, Helmut
p. 203 - 207
(2002)
Read Online

Exceedingly Facile Ph-X Activation (X=Cl, Br, I) with Ruthenium(II): Arresting Kinetics, Autocatalysis, and Mechanisms
[(Ph3P)3Ru(L)(H)2] (where L=H2 (1) in the presence of styrene, Ph3P (3), and N2 (4)) cleave the Ph-X bond (X=Cl, Br, I) at RT to give [(Ph3P)3RuH(X)] (2) and PhH. A combined experimental and DFT study points to [(Ph3P)3Ru(H)2] as the reactive species generated upon spontaneous loss of L from 3 and 4. The reaction of 3 with excess PhI displays striking kinetics which initially appears zeroth order in Ru. However mechanistic studies reveal that this is due to autocatalysis comprising two factors: 1) complex 2, originating from the initial PhI activation with 3, is roughly as reactive toward PhI as 3 itself; and 2) the Ph-I bond cleavage with the just-produced 2 gives rise to [(Ph3P)2RuI2], which quickly comproportionates with the still-present 3 to recover 2. Both the initial and onward activation reactions involve PPh3 dissociation, PhI coordination to Ru through I, rearrangement to a η2-PhI intermediate, and Ph-I oxidative addition.
Miloserdov, Fedor M.,McKay, David,Mu?oz, Bianca K.,Samouei, Hamidreza,MacGregor, Stuart A.,Grushin, Vladimir V.
supporting information
p. 8466 - 8470
(2015/11/27)

Mechanistic study on the ruthenium-catalyzed direct amination of alcohols
The Ru-catalyzed direct amination of alcohols with ammonia was investigated for the RuHCl(CO)(PPh3)3/Xantphos system in order to gain mechanistic insight. For several Ru(II) precursor complexes the influence of different additives on catalytic performance was investigated. NMR studies revealed that the reaction of RuHCl(CO)(PPh3)3/Xantphos with the alcohol in the presence of a strong base initially formed an inactive dihydrido Ru species. However, by addition of a ketone, the dihydride was (re)activated, where the corresponding imine is the actual activator, formed by immediate condensation of the ketone with ammonia. In the absence of a base, added ketone significantly enhanced catalyst activity. Catalytically inactive RuCl2(PPh3)3 could be activated by base, demonstrating that also complexes without the CO ligand give active catalysts. On the basis of these observations a mechanism was proposed, closely related to known transfer hydrogenation mechanisms.
Pingen, Dennis,Lutz, Martin,Vogt, Dieter
supporting information
p. 1623 - 1629
(2014/05/06)

A succession of isomers of ruthenium dihydride complexes. Which one is the ketone hydrogenation catalyst?
Reaction of RuHCl(PPh3)2(diamine) (1a, diamine = (R,R)-1,2-diaminocyclohexane, (R,R)-dach; 1b, diamine = ethylenediamine, en) with KOtBu in benzene quickly generates solutions of the amido-amine complexes RuH(PPh3)2(NHC6H10NH 2), (2a′), and RuH(PPh3)2(NHCH 2CH2NH2), (2b′), respectively. These solutions react with dihydrogen to first produce the trans-dihydrides (OC-6-22)-Ru(H)2(PPh3)2(diamine) (t,c-3a, t,c-3b). Cold solutions (-20°C) containing trans-dihydride t,c-3a react with acetophenone under Ar to give (S)-1-phenylethanol (63% ee). Complexes t,c-3 have lifetimes of less than 10 min at 20° and then isomerize to the cis-dihydride, cis-bisphosphine isomers (OC-6-32)-Ru(H)2(PPh 3)2(diamine) (Δ/Λ-c,c-3a, c,c-3b). A solution containing mainly Δ/Λ-c,c-3a reacts with acetophenone under Ar to give (S)-1-phenylethanol in 20% ee, whereas it is an active precatalyst for its hydrogenation under 5 atm H2 to give 1-phenylethanol with an ee of 50-60%. Complexes c,c-3 isomerize to the cis-dihydride, trans-bisphosphine complexes (OC-6-13)-Ru(H)2(PPh3)2(diamine) (c,t-3a, c,t-3b) with half-lives of 40 min and 1 h, respectively. A mixture of Δ/Λ-c,c-3a and c,f-3a can also be obtained by reaction of 1a with KBH(Busec)3. A solution of complex c,t-3a in benzene under Ar reacts very slowly with acetophenone. These results indicate that the trans-dihydrides t,c-3a or t,c-3b along with the corresponding amido-amine complexes 2a′ or 2b′ are the active hydrogenation catalysts in benzene, while the cis-dihydrides c,c-3a or c,c-3b serve as precatalysts. The complexes RuCl2(PPh3)2((R,R)-dach) or 1a, when activated by KOtBu, are also sources of the active catalysts. A study of the kinetics of the hydrogenation of acetophenone in benzene catalyzed by 3a indicates a rate law: rate = k[c,c-3a]initial[H2] with k = 7.5 M-1 s-1. The turnover-limiting step appears to be the reaction of 2a′ with dihydrogen as it is for RuH(NHCMe 2CMe2NH2)(PPh3)2 (2c′). The catalysts are more active in 2-propanol, even without added base, and the kinetic behavior is complicated. The basic cis-dihydride c,t-3a reacts with [NEt3H]BPh4 to produce the dihydrogen complex (OC-14)-[Ru(η2-H2)(H)(PPh3) 2-((R,R)-dach)]BPh4 (4) and with diphenylphosphinic acid to give the complex RuH(O2PPh2)(PPh3) 2((R,R)-dach) (5). The structure of 5 models aspects of the transition state structure for the ketone hydrogenation step. Complex 2b′ decomposes rapidly under Ar to give dihydrides 3b along with a dinuclear complex (PPh3)2HRu(μ-η2;η4- NHCHCHNH)RuH(PPh3)2 (6) containing a rare, bridging 1,4-diazabutadiene group. The formation of an imine by β-hydride elimination from the amido-amine ligand of 2a′ under Ar might explain some loss of enantioselectivity of the catalyst. The structures of complexes 1a, 5, and 6 have been determined by single-crystal X-ray diffraction.
Abbel, Robert,Abdur-Rashid, Kamaluddin,Faatz, Michael,Hadzovic, Alen,Lough, Alan J.,Morris, Robert H.
p. 1870 - 1882
(2007/10/03)

New N,N-diisopropylcarbamato complexes of ruthenium(II) as catalytic precursors for olefin hydrogenation
During the synthesis of [Ru(O2CNiPr2) 2(PPh3)2] (1), the [RuCl2(PPh 3)3]/NHiPr2XCO2 system produces the intermediates [NH2iPr2][Ru2Cl 2(H-Cl)3(PPh3)4] (2) and [RuCl(O2C-NiPr2)(PPh3)3] (3) which have been isolated and fully characterised. Compound 2 contains the dinuclear anionic triply chloride-bridged rathenium(II) species. Compound 3 is mononuclear, the octahedral ruthenium centre being coordinated to the bidentate carbamato ligand. The reactions of compounds 1 and 3 with dihydrogen have been studied at room temperature and atmospheric pressure with respect to their catalytic hydrogenation of 1-octene. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.
Belli Dell'Amico, Daniela,Calderazzo, Fausto,Englert, Ulli,Labella, Luca,Marchetti, Fabio,Specos, Monica
(2008/10/09)

The kinetic instability of σ-bound aryloxide in coordinatively unsaturated or labile complexes of ruthenium
Reaction of RuCl2(PPh3)3 (1) or RuHCl(PPh3)3 (2) with KOAr (Ar=4-tBuC6H4) in non-alcohol solvents affords π-aryloxide derivatives Ru(η5-ArO)(o-C6H4PPh2) (PPh3) (3a) or RuH(η5-ArO)(PPh3) 2 (6a), respectively. The phenoxide analogues 3b and 6b are obtained on use of KOPh or TlOPh. Treatment of 1 with 1 equiv. KOAr in the presence of isopropanol liberates the phenol and acetone, affording clean 2 in quantitative yields. In 3:1 methanol-CH2Cl2, RuHCl(CO)(PPh3)3 (4) is also formed in small amounts. Reaction of 1 with 2 KOAr in 20% MeOH-CH2Cl2 affords a mixture of 6a and RuH2(CO)(PPh3)3 (5). In the corresponding reaction of 2 with 1 KOAr, σ-π isomerization of the σ-aryloxide ligand dominates, affording 6a·MeOH as the principal product. Treatment of 6a with ethereal HCl gives [RuH(η6-ArOH)(PPh3)2]Cl (7a); the corresponding reaction of 6b yields RuCl(η5-PhO)(PPh3)2 (8b). The crystal structures of 3a, 3b, 4, 5, 7a, and 8b are reported.
Snelgrove,Conrad,Yap,Fogg
p. 268 - 278
(2008/10/08)

Bridging Fluorides and Hard/Soft Mismatch in d6 and d 8 Complexes: The Case of [TI(μ-F)3Ru(PPh 3)3]
[RuCl2(PPh3)3] reacts with thallium(I) fluoride to give either [Tl(μ-F)3Ru(PPh3)3] (1) or [Tl(μ3-F)(μ2-Cl)2RU 2(μ2-Cl)-(μ2-F)(PPh3) 4] (2) depending on the excess of TIF used. Both 1 and 2 were fully characterized, including X-ray structure determinations. Complex 1 reacts with dihydrogen to form the known ruthenium hydride complex [Ru-(H) 2(H2)(PPh3)3] upon hydrogenolysis of the Ru-F bond. The reaction of 1 with activated alkyl bromides (R-Br) gives the corresponding alkyl fluorides and the trinuclear complex [Tl(μ 3-F)(μ2-F)(μ2-X)Ru2(μ 2-Br)(μ2-F)(PPh3)4] (X = Br, F) (3), whose structure closely resembles that of 2. However, 1 is not active as catalyst for the nucleophilic fluorination of R-Br in the presence of thallium fluoride. The effect of the bridging coordination mode of fluoride on the Ru-F bond is discussed in terms of the HSAB principle, which suggests a more general model for predicting the stability of d6 and d8 complexes containing hard ligands (such as fluoro, oxo, and amido).
Becker, Claus,Kieltsch, Iris,Broggini, Diego,Mezzetti, Antonio
p. 8417 - 8429
(2008/10/09)

PROCESS FOR HYDROGENATING UNACTIVATED IMINES USING RUTHENIUM COMPLEXES AS CATALYSTS
A process is provided for the hydrogenation or asymmetric hydrogenation of dialkyl, alkylalkenyl and dialkenyl imines of formula (II) to provide amines of formula (III), wherein, (i) R1 and R2 are optionally substituted cyclic, linear or branched alkyl or alkenyl; R3 is a hydrogen atom, a hydroxy radical, optionally substituted C1 to C8 cyclic, linear or branched alkyl or alkenyl, optionally substituted aryl; or (ii) R1 is alkyl or alkenyl, R2 is alkyl or alkenyl and the two are linked together or with R3 to form one or more rings; using a catalytic system comprising a base and a ruthenium complex containing (1) a diamine and (2) a diphosphine ligand or monodentate phosphine ligands in hydrogenation and asymmetric hydrogenation processes.
-
Page/Page column 15

(2008/06/13)

Synthesis, NMR Study, and Reactivity of Isomeric Early-Late Heterobimetallic Dihydrides. X-ray Crystal Structure of (PPh3)HRu(μ-H)(μ-PMe2C5Me 4)2(μ-Cl)ZrCl
The new isomeric ruthenium/zirconium dihydrides of the formula (PPh3)HRuH(μ-PMe2Cp*)2ClZrCl (1, 2) (Cp* = C5Me4) have been characterized by elemental analysis and NMR (1H, 31P and 1H relaxation data). Complex 1, stabilized by Cl and H bridges, has been isolated from the room temperature reaction between RutyifeXPPhsh and (PMe2Cp*)2ZrCl2. The X-ray crystallographic study of 1 revealed a bimetallic complex. The six-coordinate Ru atom and the five-coordinate Zr atom are held together by two bifunctional phosphinocyclopentadienyl ligands and by H and Cl bridges. Crystal data for 1: monoclinic space group P21/c, a = 13.901(2) A?, b = 18.205(6) A?, c = 16.633(3) A?, β= 92.43(1)°, V = 4206 A?3, Z = 4, dcalc = 1.472 g cm-3, R(F) = 0.056, Rw(F) = 0.058. Complex 2 with two H bridges and terminal Cl ligands at Ru and Zr has been obtained by an irreversible isomerization of 1 in the presence of HNEt3BPh4. This transformation has been proposed to occur through slow protonation of one of the phosphorus ligands with the five-coordinate Ru center formed by undergoing rapid pseudorotation. Complexes 1 and 2 do not react with H2, N2, or 3,3-dimethyl-but-l-ene. Treatment of 1 with 1 equiv of NaHBEt2 in C6D6 gives a mixture of new trihydrides (PPh3)HRu(μ-Cl)(μ-H)(μ-PMe2Cp*) 2ZrH (3) and (PPh3)HRu(μ-H)2(μ-PMe2Cp*) 2ZrCl (4). Complex 3 transforms to 4 upon standing in solution for a period of several days. Under the same conditions, complex 2 leads smoothly to trihydride 4. Both trihydrides are new and have been characterized by 1H, 31P NMR, and 1H NMR relaxation data. Complexes 1 and 4 are fluxional in solution at room temperature, showing hydride exchange between the terminal and bridging positions. The variable-temperature 1H NMR spectra allowed determinations of the ΔG? values of 16.4 (313 K, THF-d8) and 13.5 kcal/ mol (295 K, toluene-d8) for the exchange in complexes 1 and 4, respectively. Possible exchange mechanisms have been discussed. Complex 2 is rigid on the NMR time scale.
Bakhmutov, Vladimir I.,Visseaux, Marc,Baudry, Denise,Dormond, Alain,Richard, Philippe
p. 7316 - 7324
(2008/10/09)

Synthesis and characterization of ruthenium hydride complexes containing the bulky diphosphine 1,2-bis(diisopropylphosphino)ethane (dippe). Crystal structure of [RuH(η2-O2)(dippe)2][BPh4]
The bulky diphosphine 1,2-bis(diisopropylphosphino)ethane (dippe) reacts with [RuCl2(PPh3)3] to yield [RuCl2-(dippe)2] (1), from which the complex cis-[RuH2(dippe)2] (2) can be prepared by reaction with Na[BH4]. The hydrido-chloride complex [RuHCl(dippe)2] (3) is obtained by displacement of triphenylphosphine ligands in [RuHCl-(PPh3)3] by dippe. Complex 3 dissociates one chloride ligand in methanolic or ethanolic solutions generating the 16-electron, five-coordinate species [RuH(dippe)2]+, which can be isolated as the tetraphenylborate salt (4). This compound does not react with dinitrogen or ethylene, but it reacts with CO, CNBut, or nitriles yielding the corresponding 18-electron trans-octahedral derivatives [RuH(L)(dippe)2] [BPh4] (L = CO (5), CNBut (6), PhCN (7), or MeCN (8)). 2 also reacts with dihydrogen yielding [RuH(H2)(dippe)2] [BPh4] (9), which is only stable under a dihydrogen atmosphere. Both 2 and 9 react with dioxygen to form the hydridodioxygen complex [RuH(η2-O2)(dippe)2] [BPh4] (10), which is a rare example of dioxygen coordination at a dihydrogen-binding site. The crystal structure of 10 has been determined. Crystal data: Monoclinic system, space group P21/n, a = 16.698(2) A?, b = 15.498(2) A?, c = 20.635(4) A?, β = 103.40(1)°, and Z = 4. It represents the first structural report of a hydrido-dioxygen complex. Behavior analogies of ruthenium-dippe and ruthenium-dcpe (dcpe = 1,2-bis(dicyclohexylphosphino)ethane) complexes are also discussed.
Jiménez-Tenorio, Manuel,Puerta, M. Carmen,Valerga, Pedro
p. 3515 - 3520
(2008/10/08)

Molecular dihydrogen and hydrido derivatives of ruthenium(II) complexes containing chelating ferrocenyl-based tertiary phosphine amine ligands and/or monodentate tertiary phosphine ligands
Reactions of complexes of the type RuCl2(PPh3)(P-N) with H2 are reported, where P-N represents the chelating ferrocene-based ligands (η-C5H5)Fe(η-C5H 3(CHMeNMe2)PR2-1,2) with R = i-Pr (the isoPFA ligand) or Ph (the PPFA ligand). Depending on the solvent(s) used, and absence or presence of added base, RuCl2(PPh3)(isoPFA) (2b) generates the dinuclear η2-H2 complexes L2(η2-H2)Ru(μ-Cl) 2(μ-H)Ru(H)(PPh3)2 where L2 = isoPFA (complex 3) or L2 = (PPh3)2 (complex 4). n-Butanol solutions of RuCl2(PPh3)(PPFA) (2a) under H2 also yield 4, as well as Ru(H)Cl2(PPh3)(PPFA·H)(BuOH), a zwitterionic species containing a protonated amine moiety stabilized by coordinated n-BuOH, which is a likely intermediate in heterolytic cleavage of the H2: the complex RuH(Cl)-(PPh3)(isoPFA) (5), together with a hydrido carbonyl species, is isolated from methanol solutions of 2b. Complexes 2b, 3, 4, and 5 are characterized by X-ray crystallography; the mononuclear complexes 2b and 5 are orthorhombic with space groups F2dd and P212121, respectively. For 2b, a = 10.4316 (3) A?, b = 31.4693 (10) A?, c = 43.2963 (18) A?, V = 14213.1 (8) A?3, and Z = 16; the structure refined to R = 0.054 and Rw = 0.046 for 1783 reflections with I > 2σ(I). Corresponding crystallographic data for 5 are a = 9.915 (2) A?, b = 16.511 (4) A?, c = 21.781 (5) A?, V = 3566 (1) A?3, Z = 4, R = 0.077, and Rw = 0.079 for 2691 reflections. The essential crystallographic data for the dinuclear complex 3 have been published [Hampton, C.; et al. J. Am. Chem. Soc. 1988, 110, 6918]. The related complex 4 crystallizes in the monoclinic system, space group P21/c, with a = 15.866 (5) A?, b = 18.931 (5) A?, c = 24.472 (7) A?, β = 108.69 (2)°, V = 6963 (3) A?3, Z = 4, R = 0.078, and Rw = 0.0792 for 4507 reflections. Variable-temperature 1H- and 31P-NMR data for 3 reveal fast exchange between the η2-H2 and the μ-H at 20°C and a slower exchange of this system with the terminal hydride; corresponding data for 4 and its P(p-tolyl)3 analogue 7 show a faster exchange involving all the hydrogens. Activation parameters are determined for the exchange processes.
Hampton, Cashman R. S. M.,Butler, Ian R.,Cullen, William R.,James, Brian R.,Charland, Jean-Pierre,Simpson
p. 5509 - 5520
(2008/10/08)

New Synthesis and Molecular Structure of Potassium Trihydridotris(triphenylphosphine)ruthenate
A convenient, high yield method for the synthesis of ruthenium hydrides, including anionic ruthenium hydrides, has been developed; the molecular structure of potassium trihydridotris(triphenylphosphine)ruthenate (2) complexed with 18-crown-6-ether has been determined by single crystal X-ray diffraction.
Chan, Albert S. C.,Shieh, Huey-Sheng
p. 1379 - 1380
(2007/10/02)