cas 14564-35-3, DICHLORODICARBONYLBIS(TRIPHENYLPHOSPHINE)RUTHENIUM (II)

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METHANOL AS A HYDROGEN DONOR IN REACTIONS HOMOGENEOUSLY CATALYSED BY RUTHENIUM AND RHODIUM COMPLEXES
Under suitable conditions methanol can act as a hydrogen donor towards organic substrates, especially for the reduction of ketones to alcohols.A variety of complexes of rhodium, iridium, ruthenium, and osmium have been shown to be active for this reaction; the highest activity observed so far is that of t-phosphine-ruthenium-chloride systems such as .In all the reactions the methanol is oxidised to methyl formate; some carbon dioxide is also formed.Cyclohexanone is reduced to cyclohexanol, methyl vinyl ketone and mesityl oxide to the corresponding saturated ketones, and 4-t-butylcyclohexanone to a 4/1 mixture of the trans and cis 4-t-butylcyclohexanols; aldehydes are reduced with more difficulty and cyclohexene is comparatively unreactive.Possible mechanisms for the reaction are discussed in the light of observations of changes in the catalyst precursors that take place during the rections.The reactions with methanol are also contrasted with those in wich ethanol is used as hydrogen donor.
Smith, Thomas A.,Maitlis, Peter M.
p. 385 - 396
(1985)
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Olefin ligands II. Syntheses of 2,6-diallylpyridine (DAP) complexes of iridium(I), ruthenium(II), palladium(II) and platinum(II); crystal structures of and
The tridentate ligand 2,6-diallylpyridine (DAP) has been used to synthesize novel complexes of iridium(I), ruthenium(II), palladium(II) and platinum(II) of formulae , , ClO4, , PdCl2(DAP)2>, .All the complexes have been characterized by elemental analysis.IR, and 1H NMR spectroscopy.The molecular structures of and have been determined by single-crystal X-ray diffraction studies.Crystals of the ruthenium complex are orthorhombic, space group Pbca, with Z=8 in a unit cell of dimensions a 11.492(5), b 18.942(3), c 23.083(9) Angstroem.Crystals of the palladium complex are triclinic, space group with Z=1 in a unit cell of dimensions a 7.950(4), b 8.745(4), c 9.578(4) Angstroem, α 113.02(3), β 90.75(3), γ 116.65(3)o.Both structures were solved by Patterson and Fourier methods and refined by blocked full-matrix least-squares to R=0.0528 for 2742 observed reflections in the first complex and by full-matrix least-squares to R=0.0252 for 1948 observed reflections in the second.In the octahedral ruthenium complex, DAP acts as a tridentate ligand adopting a mer configuration and the phosphine ligand is trans to the pyridinic nitrogen, while in the trans square-planar palladium complex DAP acts as a monodentate N-donor ligand.
Vasapollo, Giuseppe,Nobile, Cosimo Francesco,Latronico, Mario,Lanfranchi, Maurizio,Pellinghelli, Maria Angela
p. 429 - 440
(1987)
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Ruthenium(II) diphosphine(phosphine)/imine/amine/CO complexes as efficient catalysts in transfer hydrogenation of ketones
Treatment of [RuCl2(CO)2]n with different phosphine ligands, four Ru(II) complexes of cis-, cis-, trans- RuCl2(CO)2L2 (L = PH(C6H11)2 (1), PPh3 (2), PPh2(C6F5) (3) and PMe3 (4)), in which 1 and 3 are novel complexes, have been generated in methylene chloride and isolated as pure compound in solid. In CH2Cl2 mixed 1:1 molar ratio of RuCl2(PPh3)3 and 1,1′-bis(diphenylphosphine)ferrocene (DPPF), and further reacted with quantitative 2-aminopyridine (ampy), 2-picolylamine (picam) and pyridine ligands, the complexes of RuCl2(DPPF)(ampy) (5), RuCl2(DPPF)(picam) (6) and RuCl2(DPPF)(Py)2 (7) were generated in situ and isolated in solid. All complexes are fully characterized by multinuclear NMR (1H, 13C, 31P and 19F), element analysis and FTIR spectroscopies. Meanwhile, the single crystal structures of 1 and 8 complexes were determined by X-ray crystallography. The observed IR and crystal data of 1 ～ 4 clearly indicate that different phosphine donor ligands occupying trans axis position of Ru(II)Cl2(CO)2 skeleton can affect the coordination carbonyl C-O bond distance (1.143(3) ? (1), 1.135(3) ? (4) and 1.131(5) ? (2)), and this interaction can be quantitatively detected by its FTIR vibration frequencies. The homogeneous hydrogenation transfer catalytic reactivity of so-synthesized complexes has been tested in a basic 2-propanol solution and they indeed perform the catalytic activities in different behavior, e.g. complexes 1 and 6 are the most active catalysts and represent maximum conversion yield (1: 90.4% and 6: 90.0%) and turnover frequency (TOF) (1 18.84 h?1 and 6 37.5 h?1) at our tested experimental condition of these two types of structural complexes, which are discussed in the details.
Ge, Sai,Zhang, Jin,Zhao, Jianguo,Ulhaq, Imran,Ma, Guibin,McDonald, Robert
p. 7 - 14
(2019)
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Kinetics and mechanism of the hydrogenolysis of a ruthenium(II) acyl complex
The kinetics of the solution hydrogenolysis of the six-coordinate Ru(II) acyl complex RuCl(COR)(CO)2(PPh3)2, where R = norbornenyl, to give RuHCl(CO)2(PPh3)2 and RCHO reveal that the proces
Joshi,James
p. 199 - 205
(1990)
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On the reactivity of tris(triphenylphosphine)triruthenium enneacarbonyl
By reaction of [Ru(CO)3P(C6H5)3]3 with CO, Ru(CO)4P(C6H5)3 has been prepared from which, with halogens (X = Cl, Br, I) or CHCl3, [RuX2(CO)2P(C6H5)3] 2 complexes were obtained. These last compounds could also be formed from [Ru(CO)3P-(C6H5)3]3 and halogens. From the ir spectral data a structure with bridging halogens is suggested for the dimeric compounds [RuX2(CO)2P(C6H5)3] 2. [Os(CO)3P(C6H5)3]3 reacts with CO with displacement of P(C6H5)3 and formation of [Os(CO)4]3.
Piacenti,Bianchi,Benedetti,Braca
p. 1815 - 1817
(1968)
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Reactions of [Ru(CO)2(PPh3)3] with alkynylphosphonium salts: A phosphinoallene complex
[Ru(CO)2(PPh3)3] reacts with either HC=CCH2Br or [HC=CCH2SMe2]Br to provide the σ-allenyl complex [Ru(CH=C=CH2)Br(CO)2(PPh 3)2]; however, with [HC=CCH2PPh3]Br, the salt [Ru(γ2-H2C=C=CHPPh3)(CO) 2(PPh3)2]Br is obtained, which may be described as a complex of a phosphonioallene on the basis of crystallographic data for [Ru(γ2-H2C=C=CHPPh3)(CO) 2(PPh3)2]2Br(PF6) and a comparison of spectroscopic data with those for the simple allene complex [Ru(γ2-H2C=C=CH2)(CO) 2(PPh3)2].
Ang, Wee Han,Cordiner, Richard L.,Hill, Anthony F.,Perry, Tamara L.,Wagler, Joerg
p. 5568 - 5574
(2009/12/08)

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].
Hill, Anthony F.,Rae, A. David,Schultz, Madeleine,Willis, Anthony C.
p. 1325 - 1338
(2008/10/09)

Synthesis, characterization, reactivity and theoretical studies of ruthenium carbonyl complexes containing ortho-substituted triphenyl phosphanes
A series of ruthenium o-phosphane complexes was synthesized and characterized. The reactivity of the prepared complexes was studied by using them as catalysts for the hydroformylation of 1-hexene. The activities depended on the binding mode of the phosphane and on the strength of the ruthenium-phosphane interaction. Strongly coordinated chelating [2-(dimethylamino)phenyl]-(diphenyl) phosphane and [2-(methylthio)phenyl]- (diphenyl) phosphane showed poor activity, while weakly chelated [2-(methoxy)phenyl]-(diphenyl) phosphane and non-chelating phosphanes such as [2-(methyl)phenyl]-(diphenyl) phosphane or [2-(ethyl)phenyl]-(diphenyl) phosphane led to higher activities.
Moreno, M. Andreina,Haukka, Matti,J??skel?inen, Sirpa,Vuoti, Sauli,Pursiainen, Jouni,Pakkanen, Tapani. A.
p. 3803 - 3814
(2007/10/03)

Binuclear ruthenium macrocycles formed via the weak-link approach
The weak-link approach for the synthesis of metallomacrocycles has been used to synthesize a series of novel Ru(II) macrocycles in high yield. RuCl2(PPh3)3 has been reacted with two different phosphino-alkyl-ether hemilabile ligands, 1,4-(PPh2(CH 2)2O)2C6H4 and 1,4-(PPh2(CH2)2OCH2) 2C6H4. The hemilabile bidentate ligand coordinates to Ru(II) centers through both the P and O atoms to form bimetallic condensed intermediates . The weak Ru-O bonds have been selectively cleaved with CO, 1,2-diaminopropane, and pyridine to yield large open macrocycles. This is the first example of the weak-link approach employed to synthesize macrocycles with Ru, and metal centers in general that have more than four coordination sites.
Khoshbin, Meisa S.,Ovchinnikov, Maxim V.,Mirkin, Chad A.,Zakharov, Lev H.,Rheingold, Arnold L.
p. 496 - 501
(2008/10/09)

Synthesis and characterization of ruthenium(II) pyrazole tertiary phosphine complexes
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Evans, E. Wynne,Atlay, Mark T.
p. 623 - 632
(2008/10/08)

A facile route to carbonylhalogenometal complexes (M = Rh, Ir, Ru, Pt) by dimethylformamide decarbonylation
Dimethyl formamide (DMF) can be a convenient source of the carbonyl ligand in the coordination chemistry of rhodium, ruthenium, iridium, and platinum. We have undertaken a thorough study concerning the course of this reaction. In a first step, DMF-containing complexes are produced, which is usually accompanied by chloride redistribution. Then, upon refluxing, carbonyl species in the same oxidation state are obtained, presumably as a result of HCl-mediated DMF decomposition. Provided that water levels are kept low, reduction can occur to provide the complexes [NH2(CH3)2][RhCl2(CO) 2], [NH2(CH3)2][RuCl3(CO) 2(DMF)], [RuCl2(CO)2(DMF)2], and [NH2(CH3)2][IrCl2(CO) 2]. In the case of platinum, reduction is not effective and [NH2(CH3)2][PtCl3(CO)] is obtained. No carbonylpalladium species can be synthesized in this way, the reaction producing copious amounts of colloidal metal. Adding phosphanes to these chlorocarbonyl-containing solutions allows easy, one-step syntheses of a variety of complexes.
Serp, Philippe,Hernandez, Marc,Richard, Brigitte,Kalck, Philippe
p. 2327 - 2336
(2007/10/03)

Selenolatovinylidene complexes: Metal-mediated alkynyl selenoether rearrangements
The reactions of [RuCl2(PPh3)3] and [RuCl-(PPh3)2(η-C5H5)] with PhC≡CSeiPr provide the selenolatovinylidene complexes [RuCl2{=C=C(SeiPr)Ph}(PPhs
Hill, Anthony F.,Hulkes, Alexander G.,White, Andrew J. P.,Williams, David J.
p. 371 - 373
(2008/10/08)

Synthesis and molecular structure of [RuCl{C(=CHPh)OC(=O)CH2CH3}(CO)(PPh3) 2]: A real intermediate in ruthenium complex-catalyzed selective synthesis of a (Z)-enol ester
Reaction of [RuCl(η2-O2CCH2CH3)(CO)(PPh 3)2] (1) and phenylacetylene gives [RuCl{C(=CHPh)OC(=O)CH2CH3}(CO)(PPh3) 2] (2a). The X-ray structure analysis of 2a reveals that it includes a (Z)-enol ester-like 1-propanoyloxy-2-phenylethenyl-C1,O ligand. In the catalytic addition of propanoic acid to phenylacetylene, the complex 2a acts as a real intermediate that gives (Z)-2-phenylethenyl propanoate, selectively. The presence of the free PPh3 in the reaction mixture depresses formation of some dicarbonylruthenium species that catalytically produce (E)- and Markovnikov-type enol esters.
Kawano, Hiroyuki,Masaki, Yoshiko,Matsunaga, Takahiro,Hiraki, Katsuma,Onishi, Masayoshi,Tsubomura, Taro
p. 69 - 77
(2007/10/03)

Tetravalent tellurium ligands
Oxidative addition of TeCl4 to Vaska's complex gave the trichlorotelluronium complex [IrCl2-(TeCl3)(CO)(PPh3)2] (structure depicted), which contains a rare example of a structurally characterized tetravalent tellurium ligand. The coordination at the Te(IV) center is - in full agreement with the VSEPR model - distorted trigonal bipyramidal.
Dyson, Paul J.,Hill, Anthony F.,Hulkes, Alexander G.,White, Andrew J. P.,Williams, David J.
p. 512 - 514
(2007/10/03)

Carbonylation reactions of Rh(PPh3)3Cl and Ru(PPh3)3Cl2 in the solid state
The carbonylation reactions of Rh(PPh3)3Cl (1) and Ru(PPh3)3Cl2 (2) in the solid state with carbon monoxide at atmospheric pressure were studied; the known complexes Rh(PPh3)2(CO
Porta, Francesca,Tollari, Stefano,Bianchi, Claudia,Recchia, Sandro
p. 79 - 83
(2008/10/08)

Ruthenium-catalyzed aldol and Michael reactions of nitriles. Carbon-carbon bond formation by α-C-H activation of nitriles
The ruthenium(II)-catalyzed reaction of nitriles with carbonyl compounds proceeds highly efficiently under neutral and mild conditions to give α,β-unsaturated nitriles. Under similar reaction conditions, nitriles react with olefins bearing electron-withdrawing groups to give the corresponding Michael adducts. The efficiency of the reaction is illustrated by the selective additions to α,β-unsaturated aldehydes and acetylenes bearing electron-withdrawing groups, which are difficult to perform using conventional bases. Chemoselective aldol and Michael reactions of nitriles can be performed in the presence of other active methylene compounds. Tandem Michael and Michael-aldol condensations of nitriles 30 can be performed with high diastereoselectivity. These reactions can be rationalized by assuming oxidative addition of ruthenium(0) to the α-C-H bond of nitriles and subsequent insertions to carbonyl compounds or olefins. As the key intermediates and active catalysts hydrido(N-bonded enolato)ruthenium(II) complexes, mer-RuH(NCCHCO2R)(NCCH2CO2R)(PPh3)3 (R = Me (41a), Et (41b), n-Bu (41c)) have been isolated upon treatment of RuH2(PPh3)4 (3) or RuH(C2H4)(PPh3)2(PPh2C6H4) (4) with alkyl cyanoacetates. Kinetic study of the catalytic aldol reaction of ethyl cyanoacetate with benzaldehyde indicates that the rate-determining step is the reaction of enolato complex 41 with aldehydes.
Murahashi, Shun-Ichi,Naota, Takeshi,Taki, Hiroshi,Mizuno, Masahiko,Takaya, Hikaru,Komiya, Sanshiro,Mizuho, Yuji,Oyasato, Naohiko,Hiraoka, Makiko,Hirano, Masafumi,Fukuoka, Atsushi
p. 12436 - 12451
(2007/10/03)

Synthesis of 2-pyrrolyl complexes of ruthenium and osmium via hydrolysis of a chloro(pyrrolyl)carbene ligand or via transmetalation reactions using (2-pyrrolyl)mercuric chloride
The chloro(2-pyrrolyl)carbene complex Ru-(=C[Cl]-2-C4H3NH)Cl2(CO)(PPh 3)2 (1) undergoes hydrolysis and rearrangement to give the σ-bound 2-pyrrolyl complex Ru(2-C4H3NH)Cl(CO)2(PPh3) 2 (2). Compound 2, and the osmium analogue Os(2-C4H3NH)Cl-(CO)2(PPh3) 2 (4), can be prepared by reaction of (2-pyrrolyl)mercuric chloride (3) with the low-oxidation-state compounds M(CO)2(PPh3)3 (M = Ru, Os), respectively. Key steps in the synthesis of compound 3 involve protection of the pyrrolic nitrogen atom with a lithio-carboxylate function followed by selective lithiation and then mercuration in the ring 2-position.
Ng, Mabel M. P.,Roper, Warren R.,Wright, L. James
p. 2563 - 2565
(2008/10/08)

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.
Jessop, Philip G.,Rettig, Steven J.,Lee, Chung-Li,James, Brian R.
p. 4617 - 4627
(2008/10/08)

Reactions of α-phenylethynyl-trans-β-styryl complexes with isonitriles: hemi-labile alkyne coordination
Treatment of the complex CPh)=CHPh>Cl(CO)(PPh3)2> (1) with one equivalent of CNR (R = tBu, C6H3Me2-2,6) gives CPh)=CHPh>Cl(CNR)(CO)(PPh3)2>.Addition of a further equivalent of isonitrile and PF6 leads to the salts CPh)=(CHPh>Cl(CNR)2(CO)(PPh3)2>PF6 and the mixed species CPh)=CHPh>(CO)(CNtBu)(CNC6H3Me2-2,6)(PPh3)2>PF6.The related CPh)=CHPh>(CNtBu)(CO)2(PPh3)2>PF6 is obtained by successive treatment of with diphenylbutadiyne, hexafluorophosphoric acid and isonitrile or of 1 with carbon monoxide, AgPF6, and CNtBu.
Hill, Anthony F.,Melling, Richard P.,Thompsett, Andrew R.
p. C8 - C11
(2007/10/02)

Substituted ketene elimination from acid chlorides induced by ruthenium(0) compounds
The compound Ru(CO)2(triphos) (triphos=MeC(CH2PPh2)3) reacts with a number of acid chlorides RR'CHCOCl to form Cl and the corresponding substituted ketenes RR'CCO.A quantitative study of the reaction of Ph2CHCOCl shows that Ph2CCO is formed in a 1:1 stoichiometry.The compound Ru(CO)3(PPh3)2 also reacts with Ph2CHCOCl forming Ph2CCO and the unstable hydride Cl, the chemistry of which is also reported.
Singh, Shanti,Baird, Michael C.
p. 255 - 260
(2007/10/02)

Kinetic and thermodynamic stabilities of the geometric isomers of (R3P)2Ru(CO)2Cl2 and (R3P)3Ru(CO)Cl2 complexes
A series of ruthenium(II) complexes of the type RuCl2(CO)2P2 (P = Bzl3P, Ph3P, Ph2MeP, PhMe2P, Me3P) have been prepared and characterized by elemental analyses, physical properties, infrared spectroscopy, UV-visible spectroscopy, and 1H, 13C{1H} and 31P{1H} NMR spectroscopy. The first-formed complex, with all ligand pairs trans (ttt), thermally isomerizes in solution to produce the isomer with all ligand pairs cis (ccc). This ccc isomer further isomerizes in solution to produce the thermodynamically preferred isomer with only the phosphine ligands trans (cct). The size and basicity of the phosphine affect the isomerization rate, which increases with an increase in size and a decrease in phosphine basicity and proceeds by initial dissociation of carbon monoxide. Activation parameters, ΔS? and ΔV?, are both positive for the ttt-ccc isomerization consistent with a dissociative process. Negative values of ΔS? for the ccc → cct isomerization suggest that an associative step may be important, cis- and trans-RuCl2(CO)P3 complexes with meridionally coordinated phosphines (P = Me3P, PhMe2P, Ph2MeP) were also prepared and characterized by the same methods. The first-formed isomer with trans chlorides thermally isomerizes in solution to the thermodynamically stable isomer with cis chlorides. Positive values of both ΔS? and ΔV? are consistent with a dissociative process. Phosphine inhibition of this isomerization indicates initial phosphine dissociation. The crystal structures of cis(1)- and trans-RuCl2(CO)(Ph2MeP)3 (1 and 2, respectively) have been determined by counter methods. Compound 1 crystallizes in space group P1 with a = 16.158 (4) A?, b = 18.361 (3) A?, c = 13.170 (4) A?, α = 93.36 (2)°, β = 108.03 (3)°, γ = 90.75 (2)°, and Z = 4. Compound 2 crystallizes in space group P21/c with a = 20.373 (9) A?, b = 9.831 (5) A?, c = 20.689 (7) A?, β = 117.43 (3)°, and Z = 4. Both structures were refined by least-squares methods with R = 0.093 for 1 and R = 0.069 for 2 for 4614 and 2974 unique reflections with I/σ(I) ≥ 3.0 for 1 and 2, respectively. The bond distance of the phosphine trans to carbon monoxide in the trans isomer (d(RuP) = 2.490 (4) A?) is longer than the other two Ru-P distances (2.403 (4) A?). The 31P{1H} NMR data also suggest that this phosphine is relatively weakly bound and so this phosphine likely dissociates as the first step in the geometric isomerization.
Krassowski, Daniel W.,Nelson, John H.,Brower, Kay R.,Hauenstein, Dale,Jacobson, Robert A.
p. 4294 - 4307
(2008/10/08)

Observations regarding the mechanisms of O atom transfer from metal nitro ligands to oxidizable substrates
New experimental evidence is presented related to the mechanism of O atom transfer from metal nitro complexes to alkenes and carbon monoxide. Oxidation of alkenes by the nitro complex (py)CoTPPNO2 in the presence of Pd(CH3CN)2Cl2 as a cocatalyst is found to give product distributions that do not exactly match those expected for the simple intermolecular bimetallic O atom transfer originally proposed. Pyridine, nitro, and nitrosyl ligand exchange between the cobalt and palladium are found to be facile. In one plausible revised mechanism, the bimetallic alkene oxidation could therefore proceed via nitro group transfer to palladium, oxidation via the same metallacycles as for the monometallic Pd(CH3CN)2ClNO2 catalyst, and transfer of the resulting nitrosyl ligand back to cobalt. Several other complex mechanisms cannot be ruled out. Other systems were also investigated, but no evidence could be found for a bimetallic open-chain intermediate formed by intermolecular addition of a metal nitro complex to a coordinated alkene. A literature claim for intermolecular O atom transfer from metal nitro groups to carbon monoxide based on isotopic double-labeling experiments is incomplete due to the absence of suitable control experiments. Attempts to carry out the requisite controls were hampered by experimental limitations, but the results obtained again show that there is no compelling evidence for intermolecular O atom transfer from a metal nitro group.
Andrews, Mark A.,Chang, Tony C.-T.,Cheng, Chi-Wen F.
p. 268 - 274
(2008/10/08)

THE RUTHENIUM-CATALYSED CONVERSION OF METHANOL INTO METHYL FORMATE
Heating of methanol with yields methyl formate and hydrogen, together with some dimethoxymethane; at the end of the reaction much of the catalyst is present as the dinuclear cation, +.
Smith, Thomas A.,Aplin, Richard P.,Maitlis, Peter M.
p. C13 - C14
(2007/10/02)

Reactions of Trithiazyl Trichloride with Ruthenium, Rhodium and Iridium Complexes
The syntheses of the thionitrosyls and other complexes by the reactions of Ru(CO)3(PPh3)2, RhH(PPh3)4, Rh(NO)Br2(PPh3)2 and IrHCl2(PPh3)3 with trithiazyl trichloride are described.The new complexes obtained have been characterized by elemental analyses, IR, conductivity and magnetic data.
Jain, K. C.,Agarwala, U. C.
p. 336 - 337
(2007/10/02)

Preparation of binuclear complexes using 2-(diphenylphosphino)pyridine as a bridging ligand. Synthesis of some ruthenium complexes and their interaction with palladium complexes
The reactions between Ru(Ph2Ppy)2(CO)3 and (1,5-cyclooctadiene)PdCl2 and between Ru(Ph2PPy)2(CO)2Cl2 and Pd2-(dibenzylideneacetone)3 have been examined as routes to binuclear Ru/Pd complexes. The first reaction produces Ru-(Ph2Ppy)2(CO)2Cl2, Ru(Ph2Ppy)(CO)2Cl2, Pd2(Ph2Ppy)2Cl2, and two isomers of RuPd(Ph2Ppy)2(CO)2Cl2, while the second forms predominantly the two binuclear products. Syntheses of Ru3(CO)9(Ph2Ppy)3, Ru(Ph2Ppy)2(CO)3, and Ru-(Ph2Ppy)2(CO)2Cl2 from Ru3(CO)12 are reported as are the preparations of Pd(Ph2Ppy)2Cl2 and Pd2(Ph2Ppy)2Cl2. All new compounds have been characterized by infrared spectroscopy and 31P{1H} NMR spectroscopy. The two isomers of RuPd(Ph2Ppy)2(CO)2Cl2 interconvert on heating in solution. The structure of one isomer has been determined unambiguously by X-ray crystallography. RuPd(Ph2Ppy)2(CO)2Cl2 crystallizes in the space group P21/c with cell dimensions (determined at 140 K) of a = 10.493 (2) ?, b = 17.685 (4) ?, c = 21.470 (5) ?, β = 92.07 (2)°, Z = 4, and V = 3982 (1) ?3. The structure was refined by blocked cascade least-squares to a conventional R value of 0.043 by using 4605 significant reflections. The compound possesses a Pd-Ru bond with a distance of 2.660 (1) ?. The palladium atom is four-coordinate with a Ru, Cl, P, N donor set, while the ruthenium atom is six-coordinate with a Pd, Cl, P, N, C2 donor set.
Maisonnet, Andre,Farr, James P.,Olmstead, Marilyn M.,Hunt, Catherine T.,Balch, Alan L.
p. 3961 - 3967
(2008/10/08)

DIFLUOROCARBENE COMPLEXES OF RUTHENIUM DERIVED FROM TRIFLUOROMETHYL COMPOUNDS. RuCl2(CF2)(CO)(PPh3)2, RuCl2(CFNMe2)(CO)(PPh3)2, RuCl2(CFOMe)(CO)(PPh3)2 AND THE STRUCTURE OF Ru(CF3)(HgCF3)(CO)2(PPh3)2
Ru(CO)3(PPh3)2 or Ru(CO)2(PPh3)2 with Hg(CF3)2 gives Ru(CF3)HgCF3)(CO)2(PPh3)2.X-ray crystal structure determination reveals an octahedral geometry and the average C-F distance in the CF3 group which is Ru-bound is 0.1 Angstroem longer than in the CF3 group Hg-bound.This and other Ru-CF3 complexes such as Ru(CF3)Cl(CO)2(PPh3)2 react with aqueous acids converting the CF3 group to a CO group.Difluorocarbene complexes are implicated in these reactions and a crystalline example of such a compound is RuCl2(CF2)(CO)(PPh3)2 derived from Ru(CF3)Cl(CO)(MeCN)(PPh3) and dry HCl gas in benzene solution.RuCl2(CF2)(CO)(PPh3)2 is readily hydrolysed to RuCl2(CO)2(PPh3)2, while Me2NH gives RuCl2(CFNMe2)(CO)(PPh3)2, MeOH gives RuCl2(CFOMe)(CO)(PPh3)2, and ethanediol gives .
Clark, G.R.,Hoskins, S.V.,Roper, W.R.
p. C9 - C12
(2007/10/02)

REACTIONS OF A DICHLOROCARBENE-RUTHENIUM COMPLEX, RuCl2(CCl2)(CO)(PPh3)2
The dichlorocarbene ligand, in the new complex RuCl2(CCl2)(CO)(PPh3)2, readily undergoes substitution reactions in which the integrity of the metal-carbon bond is maintained.Reactions with species H2X (X=O, S, Se) give chalcocarbonyl complexes RuCl2(CX)(CO)(PPh3)2 while RXH (X=O, S) give new carbene complexes RuCl2(CO)(PPh3)2.Ammonia reacts to give a cyanide-containing complex, RuCl(CN)(CO)(NH3)(PPh3)2, and primary amines, an isocyanide complex, or in the case of certain primary diamines cyclic carbene complexes.RuCl2(CNNMe2)(CO)(PPh3)2 is formed in the reaction with N,N-dimethylhydrazine.Secondary amines, R2NH, react to give chloroaminocarbene complexes, RuCl2(CO)(PPh3)2.
Roper, W. R.,Wright, A. H.
p. C59 - C63
(2007/10/02)

Interaction of Nitrosyl Chloride, Bromide, Nitrite and of Nitrosyl Tribromibe with Ruthenium Complexes
The reactions of Ru(CO)3(PPh3)2 and RuHCl(CO)(PPh3)3 with NOCl, NOBr, NOBr3 and dinitrogen trioxide or NONO2 are described.The products have been characterized by elemental analyses, IR, conductivity and magnetic data.
Jain, K. C.,Pandey, K. K.,Agarwala, U. C.
p. 1124 - 1126
(2007/10/02)