35880-54-7

Upstream product

• 56144-64-0 dicarbonylchlorohydridobis(triphenylphosphine)ruthenium(II) 
• 6674-22-2 1,8-diazabicyclo[5.4.0]undec-7-ene 
• 14564-35-3 cis-dicarbonyldichlorobis(triphenylphosphine)ruthenium(II) 
• 603-35-0 triphenylphosphine 
• 239076-83-6 cis-RuH₂(CO)2(PPh₃)2 
• 20567-11-7 cis,cis,trans-RuCl₂(CO)2(PEt₃)2 
• 35828-06-9 [Ru(η-diphenylacetylene)(CO)2(triphenylphosphine)2] 
• 31267-49-9 [Ru(acetate)2(CO₂)(PPh₃)2] 
• 201230-82-2 carbon monoxide 
• 1450823-66-1 [ruthenium(hydride)(η¹-NPh2)(carbonyl)(PPh3)2] 
• 1450823-65-0 [ruthenium(hydride)(η⁵-C6H5NPh)(PPh3)2] 
• 61817-37-6 hydrido(π-phenoxo)bis(triphenylphosphine)ruthenium(II) 
• 25360-32-1 carbonyl bis(hydrido)tris(triphenylphosphine)ruthenium(II) 
• 36712-21-7 methyl [carboxyl-¹³C]benzoate 

Downstream Products

• 32240-63-4 dicarbonyldichlorobis(triphenylphosphine)ruthenium(II) 
• 14564-35-3 all-trans-[RuCl₂(CO)2(PPh₃)2] 
• 14564-35-3 cis-dicarbonyldichlorobis(triphenylphosphine)ruthenium(II) 
• 14741-36-7 [Ru(CO)3(triphenylphosphine)2] 
• 20332-49-4 tricarbonylbis(triphenylphosphine)ruthenium⁽⁰⁾ 
• 107031-78-7 cis,cis,trans-hydrido((Et)thiolato)(carbonyl)2(triphenylphosphine)2ruthenium(II) 
• 107031-85-6 cis,cis,trans-hydrido(mercapto)(carbonyl)2(triphenylphosphine)2ruthenium(II) 
• 136823-98-8 cis,cis,trans-bis((pMe)thiolato)(carbonyl)2(triphenylphosphine)2ruthenium(II)*THF 
• 107031-82-3 cis,cis,trans-hydrido((pMeC₆H₄)thiolato)(carbonyl)2(triphenylphosphine)2ruthenium(II) 
• 134290-01-0 {Ru(η2-C(CCC6H5)CHC6H5)(CO)2(P(C6H5)3)2} 
• 136823-89-7 cis,cis,trans-hydrido((Me)thiolato)(carbonyl)2(triphenylphosphine)2ruthenium(II) 
• 131821-22-2 ruthenium (η2-tetrafluoroethylene)(carbonyl)2(triphenylphosphine)2 
• 107031-79-8 cis,cis,trans-hydrido((PhCH₂)thiolato)(carbonyl)2(triphenylphosphine)2ruthenium(II) 
• 131914-95-9 ruthenium (maleic anhydride)(carbonyl)2(triphenylphosphine)2 

Relevant academic research and scientific papers

Exploring the variable hapticity of the arylamide ligand: Access to σ-amidophenyl and π-cyclohexadienylimine structures

A study of the preference for σ vs π coordination of the arylamido ligand to a late transition metal shows that LiNPh2 reacts with RuHCl(PPh3)3 (1) to yield the bent-seat piano-stool complex RuH[(η5-C6H5)NPh](PPh 3)2 (2a) but with RuHCl(CO)(PPh3)3 (3) to yield the σ-amide RuH(η1-NPh2)(CO) (PPh3)2 (4). The stability of the σ-bound NPh 2 ligand in 4 reflects the π acidity of the CO ligand, which inhibits PPh3 loss. Carbonylation of 2a at 50 C affords Ru(CO) 3(PPh3)2 (8) and HNPh2, suggesting sequential π → σ isomerization and reductive elimination. The phenoxide ligand behaves similarly: RuH(η5-C6H 5O)(PPh3)2 (2b) is formed from 1 but RuH(η1-OPh)(CO)(PPh3)3 (5) is formed from 3, and carbonylation of 2b gives 8 and phenol, although more forcing conditions are required (90 C). The crystal structure of 2a is reported.

Bis(alkynyl), metallacyclopentadiene, and diphenylbutadiyne complexes of ruthenium

Heating diphenylbutadiyne with [Ru(CO)2(PPh3) 3] or [Ru(CO)3(PPh3)2] in toluene under reflux provides respectively the ruthenacyclopentadiene [Ru{κ2-CR=CPhCPh=CR}(CO)2(PPh3) 2] (R = C≡CPh) or the cyclopentadienone complex [Ru{η4-O=CC4Ph2R2}(CO) 2(PPh3)], the latter via [2 + 2 + 1] alkyne and CO cyclization. The bis(alkynyl) complex cis,cis,trans-[Ru(C≡CPh) 2(CO)2(PPh3)2] is not formed in either of these reactions but is the product of the reaction of [RuCl 2(CO)2(PPh3)2] with LiC≡CPh or of cis,-mer-[Ru(C≡CPh)2(CO)(PPh3)3] with CO. Although the bis(alkynyl) complex does not undergo reductive elimination to provide the diyne complex, thermolysis of cis,cis,trans-[Ru(C≡CPh) (HgC≡CPh)(CO)2-(PPh3)2] (obtained from [Ru(CO)2(PPh3)3] and [Hg(C≡CPh) 2]) provides a noninterconvertible 1:1 mixture of cis,cis,trans-[Ru(C≡CPh)2(CO)2(PPh3) 2] and [Ru(η-PhC≡CC≡CPh)(CO)2(PPh 3)2].

Instant base-promoted generation of Roper's-type Ru(0) complexes Ru(CO)2(PR3)3 from a simple carbonylchlororuthenium(II) precursor

An uncommon synergism in the concerted action of OH- and PR3 toward the simple Ru(II) complex Ru(CO)3Cl2(thf) allows a highly efficient reduction of the metal in ethanol or acetonitrile solution at 0 °C, with selective production of the corresponding Roper's-type Ru(0) complexes Ru(CO)2(PR3)3 in high yields within 10 min. Copyright

Thiocarbamoyl complexes of ruthenium(II), rhodium(III), and iridium(III)

The reaction of [Ru(CO)2(PPh3)3] (1) or [Ru(η2-CS2)(CO)2(PPh3) 2] with N,N-dimethylthio-carbamoyl chloride provides [Ru(η2-SCNMe2)(CO)2(PPh2) 2]Cl (2·C1), thermolysis of which yields [Ru(η 2-SCNMe2)Cl(CO)(PPh2)2] (3). Treatment of 2·C1 with NaBH4 leads to carbonyl substitution and formation of [RuH(η2-SCNMe2)(CO)(PPh 3)2] (4), which is readily converted to an alternative isomer of [RuCl(η2-SCNMe2)(CO)(PPh3) 2] (5, Cl trans to S) on treatment with hydrochloric acid. The reaction of 2·PF6 with Na[S2CNMe2] gives [Ru(η2-SCNMe2)(k2-S2CNMe 2)(CO)(PPh3)] (6), which is also the product of the reaction of 1 with {Me2NC(S)}2S. [Ru(η2- SCNMe2)(CNC6H3Me2-2,6)(CO)(PPh 3)2]Cl (7·C1) is isolated from the reaction between [Ru(CNC6H3Me2-2,6)(CO)(PPh3) 3] and Me2NC(S)Cl. [RhCl(CO)(PPh3) 2], [RhCl(PPh3)3], or [Rh-(cod)(PPh 3)2]PF6 (cod = cycloocta-l,5-diene) react with N,N-dimethylthiocarbamoyl chloride to provide [Rh(η2-SCNMe 2)Cl2(PPh3)2] (8), while [RhCl(CS)(PPh3)2] provides the metallacyclic complex [Rh{k2-=C(NMe2)SC(=S)}Cl2(PPh3) 2] (9). The complexes [IrCl(CA)(PPh3)2] react with Me2NC(=S)Cl to give the salts [Ir(η2-SCNMe 2)Cl(CA)(PPh3)2]Cl (A = O 10·C1, S 12·C1). Photolysis of 10·C1 or treatment with dimethylamine provides the neutral complex [Ir(η2-SCNMe2)Cl 2(PPh3)2] (11), which may be obtained directly by reaction of [IrCl(N2)(PPh3)2] with Me 2NC(S)Cl. Treatment of 10·C1 with NaBH4 or NaOEt proceeds via attack at the CO ligand to form [Ir(η2-SCNMe 2){η1-C(=O)H}Cl(PPh3)2] (13) or [Ir(η2-SCNMe2){η1-C(=O)OEt}-Cl(PPh 3)2] (14), respectively.

Reactions of ruthenium(o) phosphine complexes with diphenylacetylene

Heating diphenylacetylene with [Ru(CO)2(PPh3) 3] in toluene under reflux provides the 2-phenylindenone complex [Ru(η3=CCPh=CHC6H4)(CO)(PPh 3)2], arising from C-H activ

Isomerization of olefins by phosphine-substituted ruthenium complexes and influence of an 'additional gas' on the reaction rate

Phosphine-substituted ruthenium carbonyls have often been used as catalytic precursors in reactions such as the hydrogenation or the hydroformylation of olefins. To collect evidence on the coordination of the olefin as a preliminary step of these reactions we have investigated the isomerization of hex-1-ene, in hydrocarbon solvent, in the presence of the phosphine-substituted ruthenium carbonyls Ru(CO)3(PR3)2, Ru3(CO)9(PR3)3 and Ru(CO)2(OAc)2(PR3)2 [R=Bu, Ph]. When using Ru(CO)3(PPh3)2 the rate of the reaction shows a partial first order with respect to the concentration of the catalyst and of the substrate. The activation parameters were also evaluated and the activation entropy is negative. A reaction scheme involving the displacement of a carbonyl ligand with formation of a π-olefin-ruthenium complex is suggested. The rate of the reaction significantly changes if an alcohol is used as solvent. This behaviour is attributed to a modification of the catalytic precursor with formation of a ruthenium hydride. This hypothesis is confirmed by the identification of an alkoxy ruthenium hydride. The isomerization of olefins by phosphine-substituted ruthenium carbonyls is retarded by the presence of an 'additional gas' such as dinitrogen. This influence is more evident than the analogous one reported in the hydroformylation reaction: the same pressure of the 'additional gas' present in the reaction vessel reduces the rate of the isomerization to a larger extent, i.e. the presence of 1000 bar of nitrogen decreases in otherwise identical experiments the isomerization conversion of hex-1-ene from 95.6% to 25.8%. An analogous effect is also caused by the presence of argon and xenon. Helium, on the other hand, does not display any influence. These data are an indication of an interaction between the 'additional gas' and a catalytically active transition metal complex.

An NMR study on the ruthenium complex-catalyzed C-H/olefin coupling reaction

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.

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]

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.

Competition between steric and electronic control of structure in Ru(CO)2L2L′ complexes

Magnesium reduction of RuCl2(CO)2L2 in the presence of equimolar L in THF gives Ru(CO)2L3 (L = PPh3 (1), PMePh2 (2), PEt3 (3), PiPr2Me (4)). The corresponding reduction of RuCl2(CO)2(PEt3)2 in the presence of equimolar L′ (L′ = P(2-furyl)3 (5) or AsPh3 (6)) gives Ru(CO)2(PEt3)2L′ but gives a mixture of Ru(CO)2(PEt3)3-nLn (n = 0-3) species when L′ = PPh3. Comparisons show that 3 or 5 reacts slowly with L″ = (H)2, CO, or PhC≡CPh to form Ru(CO)2L″(PEt3)2 and free PEt3 or P(2-furyl)3 but rapidly with 4 or 6 to give the analogous products. The reaction of PhC≡CPh with Ru(CO)2(PEt3)2L′ is faster for L′ = PEt3 than for P(2-furyl)3. All of these reactions are proposed to take place by preliminary ligand loss of L′, this being slower for 3 and 5 than for 1, 4, and 6. Reaction of O2 with complexes containing the readily dissociated L′ species gives simply Ru(η2-O2)(CO)2L2, but for Ru(CO)2-(PEt3)3, this is accompanied by an apparent bimolecular electron transfer involving the intact complex to give Ru(CO)(CO3)(PEt3)3. X-ray structure determinations of Ru(CO)2(PEt3)3 (bis equatorial CO in trigonal bipyramid (TBP)), Ru(CO)2(PiPr2Me)3 (two isomers: bis axial CO in TBP and also square pyramidal), and Ru(η2-PhCCPh)(CO)2(PEt3)2 (cis carbonyls and trans phosphines) are reported. It is shown that all of the Ru(CO)2L3 species exist in solution as two isomers in rapid equilibrium. Ab initio MP2 calculations on the unhindered Ru(CO)2-(PH3)3 model shows a preference for a trigonal bipyramidal structure with only a weak preference for CO to be at the equatorial site. It is shown that this pattern cannot be generalized to all π-acid ligands since ethylene is calculated to have a strong preference for an equatorial site in a TBP. Integrated quantum chemical and molecular mechanics calculations on Ru(CO)2(PEt3)3 and Ru(CO)2(PiPr2Me)3 give structures in excellent agreement with the X-ray results and confirm that the geometry and relative energetic preference for the observed structural isomers is strongly influenced, or even dominated by, the steric effect of the phosphine ligands.

Hydrido thiolato and thiolato complexes of ruthenium(II) carbonyl phosphines

Oxidative addition of RSH (R = H, alkyl, aryl) or RSSR (R = aryl) to Ru(CO)2L3 (L = PPh3, 1) yields respectively cct-RuH(SR)(CO)2L2 (type 2) (cct = cis,cis,trans) or cct-Ru(SR)2(CO)2L2 (type 3); a hydrido selenolate species is made similarly using PhSeH. Methods for in situ formation of corresponding mixed bis(thiolate) species are also given. 1 is generally unreactive toward thioethers, although with propylene sulfide cct-Ru(η2-S2) (CO)2L2 is produced. Metathesis reactions of cct-RuCl2(CO)2L2 with NaSR salts yield 3 (R = aryl) or, when R = Et, cct-RuCl(SEt)(CO)2L2 or [L(CO)2Ru(μ2 -SEt)2(μ3-SEt)Na(THF)]2 (4), depending on reaction conditions. The complexes are characterized by IR spectroscopy, 1H, 31P, and, in some cases, 13C NMR spectroscopy, and for 2g and 3g (R = SC6H4pMe) and 4, X-ray crystallography. All three complexes crystallized in the space group P1. For 2g, a = 12.340 (4) A?, b = 14.948 (3) A?, c = 10.684 (4) A?, α = 90.05 (3)°, β = 99.27 (3)°, γ = 86.84 (3)°, V = 1942 (1) A?3, and Z = 2; the structure refined to R = 0.032 and Rw = 0.037 for 7174 reflections with Fo2 > 3σ(Fo2). Corresponding crystallographic data for 3g are a = 13.173 (3) A?, b = 19.766 (4) A?, c = 9.770 (4) A?, α = 98.26 (2)°, β = 91.24 (3)°, γ = 78.31 (2)°, V = 2465 (1) A?3, Z = 2, R = 0.041, and Rw = 0.043 for 3597 reflections; for 4, a = 12.189 (3) A?, b = 13.124 (3) A?, c = 12.032 (4) A?, α = 99.70 (2)°, β = 110.61 (2)°, γ = 67.95 (2)°, V = 1668.4 (8) A?3, Z = 1, R = 0.039, and Rw = 0.043 for 4252 reflections. 4 has an unprecedented network of transition-metal and alkali-metal ions bridged by thiolate ligands: four thiolates bridge one Ru and one Na, and two thiolates bridge one Ru and two Na atoms. The geometries at Ru and Na are close to octahedral and square pyramidal, respectively. Trends are noted for the 1H NMR shifts and 2JPH values for the hydride in 2, and an additivity rule formulated for the 31P shift within the cct-Ru(SR)(SR′)(CO)2(PPh3)2 species. Limited kinetic data suggest that the oxidative addition reactions to 1 probably proceed via a nonradical process, following dissociation of a PPh3 ligand.