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Synthesis and structural characterisation of ruthenium and osmium carbonyl clusters containing organomercurials
Reaction of the activated cluster [Os3(CO)10(NCMe)2] with [PhHgS(C5H4N)] afforded two new Os-Hg clusters cis-[Os(CO)4{Os3(CO)10(μ-η 2-SC5H4N)(μ-Hg)}2] 1 and [{Os3(CO)10(μ-η2-SC5H 4N)}2(μ4-Hg)] 2 in 25 and 30% yields, respectively. Cluster 1 consists of two {Os3(CO)10(μ-η2-SC5H 4N)(μ-Hg)} subunits bonded to a central Os(CO)4 moiety in a cis configuration. Cluster 2 comprises two skewed Os-Hg metal butterflies sharing a common wingtip Hg atom. Treatment of the same organomercurial with [Ru3(CO)10(NCMe)2] produced the cluster compound cis-[Ru(CO)4{Ru3(CO)9(μ-η 3-SC5H4N)(μ-Hg)}2] 3 (48%). This has a metal skeleton similar to that of 2 with the {S(C5H4N)} ligand moiety bonding to the ruthenium atoms in a μ-η3 fashion. Treatment of [Os3(CO)10(NCMe)2] with [PhHg(mbt)] (Hmbt = 2-mercaptobenzothiazole) afforded [{Os3(CO)10(μ-η2-mbt)} 2(μ4-Hg)] 4 (35%) and [Os3(CO)10(μ-η2-mbt)(μ-η 2-Hg(mbt)] 5 (20%). Cluster 4 is very similar to 2, but the S(C5H4N) ligand is replaced by the mbt ligand, while 5 consists of an Os3 triangle having one edge spanned by both [μ-η2-mbt] and [μ-η2-Hg(mbt)] moieties. The reaction of [Os5C(CO)15] and [Ru3(CO)12] with another class of organomercurial (diphenylthiocarbazono)phenylmercury reagent [PhHgL′] [L′ = SC(N=NPh)(=NNHPh)] containing a N=N functionality under thermal conditions produced [{Os5C(CO)14(μ-η2-SPh)} 2(μ4-Hg)] 6 (26%) and [{Os5C(CO)14(μ-η2-L′)} 2(μ4-Hg)] 7 (34%) and [Ru2(CO)4Ph{μ-η2-C(O)Ph}(μ 2-S)(μ-η2-L′)] 8 (15%), [Ru2(CO)4(C(O)Ph) {μ-η2-C(O)Ph}(μ2-S)(μ-η 2-L′)] 9 (15%) and [{Ru(CO)2Ph}2(μ-η2-L′)] 10 (45%), respectively. In clusters 6 and 7, two {Os5C(CO)14} subunits linked by a common wingtip mercury atom, are bonded with both μ-η2-SPh in 6 and μ-η2-L′ in 7. However, in the case of complexes 8, 9 and 10, only binuclear ruthenium carbonyl complexes formed instead of the expected formation of mixed-metal clusters. Complexes 1-10 result from the cleavage of both Hg-C and Hg-S bonds in the parent organomercury species. All these complexes have been fully characterized by both spectroscopic and crystallographic techniques.
Kong, Fung-Sze,Wong, Wing-Tak
p. 2497 - 2510
(1999)
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The Reduction of (μ2-NO) in by Carbon Monoxide; Evidence for the Formation of a Triruthenium Nitrido Intermediate, and the Structural Characterisation of and
The cluster reacts with CO to form the species , , , and , evidence suggesting the formation of a reactive nitrido- or nitrene-nitrosyl intermediate; X-ray analysis shows that both of the tetranuclear nitrido species adopt a 64-electron 'butterfly' structure in which the 'hinge' metal-metal vector is long and supports a (μ2-NO) or a (μ2-NCO) bridging group.
Attard, Julian P.,Johnson, Brian F. G.,Lewis, Jack,Mace, Julian M.,Raithby, Paul R.
p. 1526 - 1528
(1985)
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Organosulphur-Transition-metal Chemistry. Part 5. Face Bonding of Cycloheptatrienyl and Cyclo-octatetraene Ligands in Sulphur-Ruthenium Clusters: Crystal and Molecular Structure of t)(μ3-(η7-C7H7))>
The sulphur-ruthenium cluster complex t)> reacts with cycloheptatriene in boiling heptane to give t)(μ3-(η7-C7H7))> and t)(μ-(η7-C7H7))>.The former contains a facebridging cycloheptatrienyl ligand, established through an X-ray diffraction study.Crystals are monoclinic, space group C2/c, with eight molecules in a unit cell of dimensions a=14.875(6), b=8.902(6), c=30.977(2) Angstroem, and β=94.785(4) deg.The structure has been solved by conventional techniques, revealing the ruthenium atoms to be present in isosceles triangular units disordered in ca. 2:1 ratio via a 60 deg rotation in the ruthenium plane.Refinement was by least squares for 3860 data to R 0.041.The ruthenium triangle is bridged on one side by a μ3-SBut ligand and on the other by a face-bonded C7H7 ring which is planar and lies parallel to the face at a distance of 2.07 Angstroem.The hydrogens of the C7H7 ligand are inclined away from the metal triangle as a result of ?-orbital reorientation.The ruthenium-carbon (ring) distances are compatible with bonding of the C7H7 ligand in η2,η2,η3 fashion to the metal triangle, each atom of which bears two terminal carbonyl groups, but n.m.r. spectra show that the ring rotates freely relative to the face in solution.The high-fild 13C n.m.r. shift (38.7 p.p.m.) for the μ3-(η7-C7H7) ligand is characteristic, comparing with 61.0 p.p.m. for similarly fluxional μ-(η7-C7H7) in t)(μ-(η7-C7H7))>.Treating t)(μ3-(η7-(C7H7))> with CO results in cluster fragmentation to yield t)(μ-(η7-C7H7))>, a reaction attributed to the ability of both SBut and C7H7 ligands to vary their mode of co-ordination.Reactions of t)> with cyclo-octatetraene, cyclo-octatriene, and cyclopentadiene also effect cluster breakdown, forming t)(μ-(η7-C8H9))> or t)(η-C5H5)2>.The sulphur-ruthenium cluster in is less easily destroyed.The reaction with cyclo-octatetrane provides 8-C8H8))>, containing rare face-bonded fluxional C8H8, while with cycloheptatriene the complexes 5-C7H9)(μ3-(η7-C7H7))>, 5-C7H9)(μ3-(η7-C7H7))>, and 7-C7H7))2> are obtained, partly characterised using the 13C n.m.r. criterion of the C7H7 bonding mode.
Cresswell, T. Anthony,Howard, Judith A. K.,Kennedy, Fiona G.,Knox, Selby A. R.,Wadepohl, Hubert
p. 2220 - 2229
(1981)
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(13)C NMR study of reorientational dynamics in Ru3(Co)9(μ(3)-Co)(μ(3)-NPh). Relaxation time analysis in the non-motional narrowing regime
The NMR (13)C spin-lattice relaxation times of the phenyl group and equatorial carbonyl carbons in Ru3(CO)9(μ(3)-CO)(μ(3)-NPh) were measured as a function of temperature and resonance frequency in the solvent methylene chloride, and at several temperatures in chloroform. Phenyl T(1)s were used to calculate the diffusion coefficients characterizing molecular tumbling, D(.perp.), and spinning of the phenyl group, D(s); carbonyl relaxation times yielded the parallel diffusion coefficient, D(.paral.). Values of D(.perp.) calculated using the standard motional narrowing assumption were incorrectly observed to be frequency dependent, and inmarked error (by as much as a factor of two) from results obtained usin g the non-motionally narrowed equations. The spinning diffusion coefficients, D(s), were an order of magnitude greater than either D(.perp.) or D(.paral.), but somewhat lower than the rate of the equivalent rotation of free benzene in the same solvents, indicating the existence of a barrier to internal rotation of the phenyl group. Fenske-Hall and extended Hueckel calculations revealed that the barrier arises primarily from steric interactions between the ortho protons of the phenyl group and the carbon atom of the equatorial carbonyls.
Wang, D.,Shen, H.,Richmond, M. G.,Schwartz, M.
p. 1 - 6
(1995)
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The Reduction of (μ2-NO) in 2-NO)> to (μ3-NH) and (μ2-NH2) by Molecular Hydrogen
- reacts with NOBF4 in moist MeCN to generate HRu3(CO)10NO, HRu3(CO)10NH2, and HRu4N(CO)12; the same products, together with H2Ru3(CO)9NH and H4Ru4(CO)12, are observed in the direct hydrogenation of HRu3(CO)10NO.
Johnson, Brian F. G.,Lewis, Jack,Mace, Julian M.
p. 186 - 188
(1984)
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PROTONATION OF (μ-H)3Ru(μ3-CR)(CO)9. EVIDENCE FOR THE FORMATION OF AN AGOSTIC METAL-HYDROGEN-CARBON BOND
Protonation of (μ-H)3(μ3-CR)(CO)9 (M = Ru, R = Et or M = Os, R = Me) by dissolution in HSO3CF3 yields H3M3(HCR((CO)9+, containing a M-H-C bridge.The products were characterized by 1H and 13C NMR spectroscopy.Decompositions of other protoned methylidyne clusters form CH3R and a variety of metal-containing products.
Bower, David K.,Keister, Jerome B.
p. C33 - C36
(1986)
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Synthesis and Characterisation of the Hexanuclear Bimetallic Cluster, (μ4-Bi)>
The bimetallic cluster 4-Bi)> has been prepared from the reaction of Bi(NO3)3.5H2O and Na in methanol, and shown by X-ray analysis to be a spiro-cluster containing a 'Ru2(CO)8' fragment connected to a 'Ru3H(CO)10' fragment by a μ4-bismuth atom with a pseudo-tetrahedral co-ordination geometry.
Johnson, Brian F. G.,Lewis, Jack,Raithby, Paul R.,Whitton, Alan J.
p. 401 - 402
(1988)
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The Chemical Activation of Iron, Ruthenium, and Osmium Carbonyl Cluster Anion-susing Oxidative Addition
The chemical activation of iron, ruthenium, and osmium carbonyl cluster anions has been achived by investigating their oxidative electrochemistry and then matching the observed electrochemical oxidation potential with chemical reagents, by the use of oxidative addition in the presence of the required ligand; the dianionic clusters (2-), Ru3(CO)11>(2-), (2-), (2-), (2-), and (2-) have been found to react with multi-electron donor ligands in the presence of a suitable oxidant.
Drake, Simon R.,Johnson, Brian F. G.,Lewis, Jack
p. 1033 - 1035
(1988)
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Behaviour of Polynuclear Ruthenium Carbonyl Carboxylates in the Presence of Hydrogen and/or Carbon Monoxide
The thermal behaviour in the temperature range 293-453 K of n3)2>, n3)2> and n3)2> in hydrocarbon solution, taken separately or in binary mixtures, with each other or with m>, under nitrogen or, alternatively, hydrogen, carbon monoxide, or their mixtures, has been monitored by i.r. spectroscopy under reaction conditions.A deficiency of ligands leads to the formation of larger clusters while their abundance in solution shifts the equilibria towards mononuclear complexes.Under carbonmonoxide the formation of ruthenium(0) complexes is obtained from the above compounds.The presence of hydrogen together with carbon monoxide seems to facilitate such evolution of the system probably through the formation of intermediate hydridic derivatives which however were not detected.
Frediani, Piero,Bianchi, Mario,Salvini, Antonella,Piacenti, Franco
p. 3663 - 3668
(1990)
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Improved Synthesis of the Hexanuclear Clusters (2-), (1-), and H2Ru6(CO)18. The X-Ray Analysis of (1-), a Polynuclear Carbonyl containing an Interstitial Hydrogen Ligand
The X-ray analyses of two crystalline modifications, (I) and (II), of are reported, together with improved synthetic routes to this and the related clusters (2-) and H2Ru6(CO)18.Crystals of (I) are triclinic, space group P1-, with a=18.083(4), b=19.101(4), c=19.238(5) Angstroem, α=117.70(4), β=78.13(2), γ=97.05(2) deg, and Z=4.Crystals of (II) are monoclinic, space group P21/n, with a=33.82(8) b=52.55(10), c=9.832(2) Angstroem, β=92.66(2) deg, and Z=12.Least square refinement using diffractometer data (Mo-Kα) has given an R of 0.0681 for 9165 reflections for (I) and an R of 0.23 (Ru only) for 1485 reflections for (II).The unit cell in (I) contains two independent molecules of (1-), cluster (1) which is ordered and cluster (2) which is disordered between two sites (2A) and (2B) that are related by a non-crystallographic two-fold axis.The combined evidence of the X-ray analyses, 1H n.m.r. studies, i.r. spectra, and variable-temperature 13C n.m.r. is only consistent with the hydrogen ligand lying inside the Ru6 octahedron.
Eady, Colin R.,Jackson, Peter F.,Johnson, Brian F. G.,Lewis, Jack,Malatesta, Maria Carlotta,et al.
p. 383 - 392
(1980)
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Surface organometallic chemistry: reductive carbonylation of silica-supported RuCl3*3H2O
The reductive carbonylation of silica-supported RuCl3*3H2O was investigated.This physisorbed salt reacts with CO at 25-50 deg C to form the silica-bound species )2>, which is converted into the silica-bound tricarbonyl species Ru(CO)3C
Roberto, Dominique,Psaro, Rinaldo,Ugo, Renato
p. 123 - 131
(1993)
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Novel polymeric carbonylhaloruthenium(I) polyanions: Rational design and self-reorganization in the presence of CO2 and H2O
We just need to mix [Ru(CO)3Cl2(thf)] with methanolic NEt4OH - nature will do the rest: The unsaturated fragments thus generated spontaneously polymerize with production of CO2 and H2O, which combine
Maurette, Luc,Donnadieu, Bruno,Lavigne, Guy
p. 3707 - 3710
(1999)
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Solution and crystal structures of the hydridoruthenium raft clusters H2Ru6(CO)15(L)(C6H4O) (L = CO, P(OMe)3)
The structures of H2Ru6(CO)15(L)(C6H4O) (L = CO, P(OMe)3) in solution (as indicated by 1H NMR studies) and in the solid state (as indicated by X-ray studies) are discussed.The two-dimensional COSEY spectrum of the unsubstituted cluster shows the presence
Bhaduri, Sumit,Sharma, Krishna,Khwaja, Hanif,Jones, Peter G.
p. 169 - 176
(1991)
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Surface-mediated organometallic synthesis: High-yield and selective syntheses of neutral and anionic ruthenium carbonyl clusters by controlled reduction of silica-supported RuCl3 in the presence of Na2CO3 or K2C
[Ru3(CO)10Cl2], [Ru3(CO)12], [H4Ru4(CO)12], [H3Ru4(CO)12]-, [HRu6(CO)18]-, and [Ru6/
Roberto, Dominique,Cariati, Elena,Lucenti, Elena,Respini, Marco,Ugo, Renato
p. 4531 - 4539
(1997)
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ROLE OF THE CATION IN THE REACTION OF Ci(CO)4- WITH RuCl3*xH2O. SYNTHESIS AND MOLECULAR STRUCTURE OF THE RUTHENIUM CLUSTER 2
Reaction of with RuCl3 * xH2O (4/1 ratio) in THF affords Ru3(CO)12, , and 2.The latter has been fully characterized by an X-ray structural analysis.These results are compared
Braunstein, Pierre,Rose, Jacky,Dusausoy, Yves,Mangeot, Jean-Paul
p. 125 - 134
(1983)
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Dimethyl sulfide substituted mixed-metal clusters. Synthesis, structure, and characterization of HRuCo3(CO)11(SMe2) and [HRuRh3(CO)9]2[SMe2]3
Ligand substitution reactions of dimethyl sulfide with mixed-metal clusters are described. The clusters HRuCo3(CO)11(SMe2) (1) and [HRuRh3(CO)9]2[SMe2]3 (2) have been prepared by reactions of SMe2 with the neutral parent clusters. Their crystal structures have been established. Dimethyl sulfide coordinates terminally as a two-electron donor on basal cobalt in 1 and as a bridging four-electron donor causing unusual dimerization of clusters in 2. The carbonyl arrangement of the parent clusters was not changed during the ligand substitution, and hydride ligands bridge the three basal metals in both compounds.
Rossi,Pursiainen,Ahlgren,Pakkanen
p. 475 - 479
(1990)
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New insight into a convenient base-promoted synthesis of Ru3(CO)12
The addition of two equivalents of KOH per Ru under 1 atm CO at 75°C to a mixture of [Ru(CO)2Cl2]n and [Ru-(CO)3Cl2]2 generated in situ by carbonylation of 5 grams of RuCl3·3H2O in 2-ethoxyethanol, triggers a reaction cascade producing Ru3(CO)12 in yields exceeding 90% within 45 minutes.
Faure, Matthieu,Saccavini, Catherine,Lavigne, Guy
p. 1578 - 1579
(2003)
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Tetranuclear butterfly cluster derivatives of SMe2. Preparation and structures of Ru4(CO)13(SMe2), H2Ru4(CO)12(SMe2), and HRu3Co(CO)12(SMe2)
The carbonyl clusters Ru4(CO)13(SMe3) (1), H2Ru4(CO)12(SMe2) (2), and HRu3Co(CO)12(SMe2) (3) have been obtained in reactions between dimethyl sulfide and tri- or tetranuclear metal carbonyl clusters. These compounds have been characterized by X-ray diffraction studies. 1 crystallizes in space group P21/n with a = 9.406 (3) ?, b = 15.393 (6) ?, c = 15.812 (6) ?, β = 92.23 (3)°, and Z = 4; 2, in space group P21 with a = 8.18 (1) ?, 6 = 15.86 (2) ?, c = 9.55 (1) ?, β = 114.6 (1)°, and Z = 2; 3, in space group P21/n with a = 9.349 (4) ?, b = 16.259 (7) ?, c = 14.469 (6) ?, β = 92.04 (3)°, and Z = 4. The compounds are butterfly clusters, in which the four-electron SMe2 ligand bridges the wing-tip positions. In 1 and 3 one of the carbonyls bridges the hinge of the butterfly; otherwise the compounds contain only terminal carbonyls. The hydrides occupy a wing and the hinge Ru-Ru bond in 2 and a wing Ru-Co bond in 3. In 3 the cobalt atom is in a hinge position. The chalcogenide derivatives of tetranuclear Ru-Co-Rh cluster compounds show a structural trend depending on the metal composition. Terminal coordination (Co4, RuCo3, and RuCo2Rh), butterfly structures (Ru4 and Ru3Co), or dimerization of clusters (RuRh3) is found.
Rossi, Sirpa,Pursiainen, Jouni,Pakkanen, Tapani A.
p. 1390 - 1394
(1991)
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Cluster chemistry. 27. The synthesis and structural characterization of three mixed gold-cobalt-ruthenium carbonyl clusters Ph3PAuCoRu3(CO)13, (Ph3PAu)2CoRu3(H)(CO)12, and (Ph3PAu)3CoRu3(CO)12
A unique series of mixed gold-cobalt-ruthenium carbonyl clusters has been prepared and structurally characterized. Reaction of [(Ph3PAu)3O]BF4 with HCoRu3(CO)13 gives the three clusters Ph3PAu-CoRu3(CO)13 (1), (Ph3PAu)2CoRu3(H)(CO)12 (2), and (Ph3PAu)3CoRu3(CO)12 (3). An alternative specific route to 3 is via [(Ph3PAu)3O]BF4 and [CoRu3(CO)13] , while Ph3PAuCl and [CoRu3(CO)13]- give exclusively 1. For 1 [C31H15O13AuCoPRu3, a = 9.345 (3) ?, b = 14.217 (4) ?, c = 14.721 (3) ?, α = 114.83 (2)°, β = 93.16 (2)° γ = 92.44°, triclinic, P1, Z = 2] a trigonal-bipyramidal core is found, with the Ph3PAu group triply bridging a CoRu2 triangle. For 2 [C48H31Au2CoO12P2Ru 3·0.5CH2Cl2, a = 35.173 (9) ?, b = 13.548 (9) ?, c = 23.193 (4) ?, β = 102.27 (2)°, monoclinic, C2/c, Z = 8] a capped trigonal-bipyramid core exists with the second Ph3PAu group capping an AuRu2 face of 1 and the hydride ligand bridging an Ru-Ru bond. The structures are rationalized in terms of the maximum number of face-sharing tetrahedra; the isolobality of H and Ph3PAu is not valid in the context of polygold clusters.
Bruce, Michael I.,Nicholson, Brian K.
p. 101 - 108
(1984)
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Preparation, Characterisation, Molecular and Crystal Structure of the Octaruthenium Arene Clusters 6-arene)> (arene = C6H6 or C16H16)
Two octaruthenium arene clusters, 6-arene)> (arene = C6H6 1 or C16H16 2), have been isolated from the thermolysis of in octane, in the presence of cyclohexene (C6H10) or paracyclophane (C16H16), respectively.Both
Braga, Dario,Grepioni, Fabrizia,Dyson, Paul J.,Johnson, Brian F. G.,Martin, Caroline M.
p. 909 - 916
(1995)
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METAL CLUSTERS IN CATALYSIS. THE REACTIVITY OF ALKYNE- AND VINYLIDENE-SUBSTITUTED HOMO- AND HETERO-METALLIC CLUSTERS TOWARDS MOLECULAR HYDROGEN IN HOMOGENEOUS CONDITIONS
The reactivity of alkyne- and vinylidene-substituted clusters towards molecular hydrogen in homogeneous conditions has been studied by means of GC and GC/MS techniques.The reactivity of the homo- and hetero-metallic cluster frames (containing nickel and one of the iron triad metals) is discussed, as well as that of the coordinated ligands.Under hydrogen the cluster cores are modified, sometimes as a part of a catalytic cycle.The products obtainable from the coordinated small molecules seem to depend mainly on the overall electronic situation of the clusters or on the C-C distances in the alkynes, and to a lesser extent on the number of coordinating metal centres.In some instances it was observed that when both free alkynes and substituted clusters were present, only the coordinated alkynes were hydrogenated.
Castiglioni, Mario,Giordano, Roberto,Sappa, Enrico
p. 217 - 234
(1983)
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The use of photogenerated intermediates in the study of cluster build-up reactions: The generation of Ru6C(CO)17 from Ru3(CO)12
The use of photochemistry in the study of cluster build-up reactions involving transition-metal carbonyl complexes has been illustrated by an investigation into the generation of the hexanuclear carbido cluster Ru6C(CO)17 from the tr
Leadbeater, Nicholas E.
p. 250 - 252
(1998)
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Iridium-Ruthenium-gold cluster complexes: Structures, and skeletal Rearrangements
Three new IrRuAu trimetallic cluster complexes: IrRu3(CO) 13AuPPh3, 1, HIrRu3(CO)12(AuPPh 3)2, 2 and IrRu3(CO)12(AuPPh 3)3, 3 were obtained in low yields from the reaction of HIrRu3(CO)13 with [(AuPPh3)3O] [BF4]. Compounds 1 and 3 were subsequently obtained in much better yields (82%) and (84%) from the reactions of [AuPPh3][NO3] and [(AuPPh3)3O][BF4] with [PPN][IrRu 3(CO)13], respectively. The molecular structures of all three compounds were established by single crystal x-ray diffraction methods. Compounds 1 and 2 contain an Au(PPh3) group that bridges one triangular face of a tetrahedral IrRu3 cluster. Compound 2 contains a second Au(PPh3) capping group that bridges an Ir-Ru-Au triangle. Compound 3 consists of a pentagonal bipyramidal Au3IrRu3 cluster that has three gold atoms and two of the ruthenium atoms in the equatorial plane. There is a bond between the apical Ir and Ru atoms. Compounds 2 and 3 exhibit dynamical activity in the metal skeleton that leads to a rapid averaging of the inequivalent Au(PPh3) groups on the NMR timescale at room temperature.
Adams, Richard D.,Pellechia, Perry J.,Smith, Mark D.,Zhang, Qiang
p. 20 - 25
(2012)
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Tri- and tetranuclear mixed-metal clusters containing alkyne ligands: Synthesis and structure of [Ru3Ir(CO)11(RCCR')]-, Rru2Ir(CO)9(RCCR')]-, and [HRu2Ir(CO)9(RCCR')]
The tetrahedral cluster anion [Ru3Ir(CO)13]- (1) reacts with internal alkynes RC≡CR' to afford the alkyne derivatives [Ru3Ir(CO)11(RCCR')]- (2: R = R' = Ph; 3: R = R' = Et; 4: R = Ph; R' = Me; 5: R = R' = Me) which have a butterfly arrangement of the Ru3Ir skeleton in which the alkyne is coordinated in a μ4-η2 fashion. Under CO pressure they undergo fragmentation to give the trinuclear cluster anions [Ru2Ir(CO)9(RCCR')]- (6: R = R' = Ph; 7: R = R' = Et; 8: R = Ph; R' = Me; 9: R = R' = Me), in which the alkyne ligand is coordinated in a μ3-η2 parallel fashion. Protonation of these trinuclear anions leads to the formation of the corresponding neutral hydrido clusters [HRu2Ir(CO)9(RC≡CR')] (10: R = R' = Ph; 11: R = R' = Et; 12: R = Ph; R' = Me; 13: R = R' = Me). The protonation of the butterfly anions 2 and 3, however, gives rise to the formation of the neutral tetrahedral clusters [HRu3Ir(CO)11(RCCR')] (14: R = R' = Ph and 15: R = R' = Et), respectively. The analogous clusters [HRu3Ir(CO)11(PhCCCH3)] (16) and [HRu3Ir(CO)11(CH3CCCH3)] (17) are only accessible from the reaction of the neutral cluster [HRu3Ir(CO)13] with the corresponding alkynes. The complexes 2, 4, 5, 6, 10, 12 and 15 are characterised by X-ray structure analysis.
Ferrand, Vincent,Suess-Fink, Georg,Neels, Antonia,Stoeckli-Evans, Helen
p. 853 - 862
(1999)
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A Transient Infrared Spectroscopy Study of Coordinatively Unsaturated Ruthenium Carbonyls
Transient infrared spectroscopy is used to study coordinatively unsaturated Ru(CO)x products formed by excimer laser photolysis of gas-phase Ru(CO)5.Both Ru(CO04 and Ru(CO)3 are photoproducts of 248- and 351-nm irradiation of Ru(CO)5.This is the first report of direct observation of unsaturated Ru(CO)x species.Unlike the well-known Fe(CO)4 fragment, the high reactivity of the Ru(CO)x species has precluded their observation in cryogenic studies.The rate constants for reaction of Ru(CO)4 and Ru(CO)3 with CO are (2.8 +/- 0.8) * 10-11 and (7.6 +/- 0.3) * 10-11cm3molec-1s-1, respectively.These rate constants are ca. 103 greater than that for the reaction of Fe(CO)4 with CO and can be rationalized in terms of the spin states of the reactants and products.Formation of a dinuclear complex, Ru2(CO)9, is also observed.Comparison of the distribution of M(CO)x fragments at different UV photolysis wavelengths has implications for the relative bond dissociation energies for carbonyl ligands on a ruthenium versus an iron center.
Bogdan, Paula L.,Weitz, Eric
p. 3163 - 3167
(1989)
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The synthesis of heteronuclear clusters containing cyclopentadienyl- or pentamethylcyclopentadienyliridium and ruthenium or osmium
The reaction of Cp*Ir(CO)2 or CpIr(CO)2 with Ru3(CO)12 under a hydrogen atmosphere afforded the heterometallic clusters Cp*IrRu3(μ-H)2(CO) 10 and CpIrRu3(μ-H)2(CO)10, respectively, in moderate yields. In the former reaction, the tetrahydrido cluster Cp*IrRu3(μ-H)4(CO)9 was also formed in trace amounts, although this cluster can be obtained in high yields by the hydrogenation of Cp*IrRu3(μ-H)2(CO) 10; the Cp analogue was not obtainable. The reaction of Os 3(μ-H)2(CO)10 with Cp*Ir(CO) 2 afforded the osmium analogue Cp*IrOs3(μ-H) 2(CO)10 in 70% yield, along with a trace amount of the pentanuclear cluster Cp*IrOs4(μ-H)2(CO) 13. Hydrogenation of Cp*IrOs3(μ-H) 2(CO)10 afforded Cp*IrOs3(μ-H) 4(CO)9 in excellent yield. The reaction of Cp*Ir(CO)2 with Os3(CO)10(CH 3CN)2 afforded the known trinuclear cluster Cp*IrOs2(CO)9 and the novel cluster Cp*IrOs3(CO)11. Solution-state NMR studies show that the hydrides in the iridium-ruthenium clusters are highly fluxional even at low temperatures while those in the iridium-osmium clusters are less so.
Srinivasan, Padmamalini,Leong, Weng Kee
p. 403 - 412
(2006)
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A General Route for the Synthesis of Tetranuclear Clusters containing Closed Triruthenium and Triosmium Triangles
The cluster compounds (M = Ru or Os, M'= Co) and (M = Ru or Os; M'= Fe, Ru, or Os) have been prepared in good yield by the reaction of an appropriate tetracarbonylmetalate with the bis(acetonitrile) complexes, M = Ru or Os).The anionic clusters have been protonated, where possible, to give the corresponding neutral hydride clusters.In addition to known tetranuclear cluster synthesised by this method, we report the new cluster compounds , , and .
Foulds, Gary A.,Johnson, Brian F. G.,Lewis, Jack,Sorrell, Robert M.
p. 2515 - 2518
(1986)
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Formation of H2Ru6(CO)17 from H2Ru6(CO)18 an improved synthesis of HRu6(CO)17 B
Spontaneous decarbonylation of the octahedral cluster H2Ru6(CO)18 produces the bicapped tetrahedral cluster H2Ru6(CO)17. The clusters H2Ru6(CO)18 and H2R6(CO)17 have strikingly similar IR and 1 H NMR spectra. In appearance they are indistinguishable; both are deep purple in color. The decarbonylation reaction is partially reversible under low pressures of CO. Reaction of H2Ru6(CO)17 with BH3S(CH3)2 provides an improved synthesis of HRu6(CO)17B, an octahedral cluster with a boron atom at the center of the Ru6 core. HRu6(CO)17B reacts with excess CO at high pressures to produce HRu4(CO)12BH2 and ruthenaboride clusters with pentanuclear metal cores that are proposed to be HRu5(CO)15B and HRu5(CO)16B.
McCarthy, Deborah A.,Bauer, Jeanette Krause,Hong, Fung-E,Oh, Jung Ran,Deng, Haibin,Liu, Jianping,Shore, Sheldon G.
p. 309 - 314
(1998)
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Synthesis and Structural Characterisation of the Hexanuclear, Bimetallic, Ladder-like Cluster HRu5Cu(CO)18PPh3
The bimetallic cluster HRu5Cu(CO)18PPh3 has been prepared by the reaction of CO with H3Ru4(CO)12CuPPh3, characterised by X-ray crystal structure analysis, and shown to contain a 'ladder-like' arrangement of Ru5Cu based on triangular units.
Evans, John,Street, Andrew C.,Webster, Michael
p. 637 - 638
(1987)
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Precursors of quadruply bridging phosphorus monoxide ligands: Synthesis and structural characterization of a new family of anionic fluoro and alkoxyphosphinidene clusters
A new family of phosphorus functionalized, pentanuclear ruthenium clusters Ru5(CO)15(μ4-PR) [R = NiPr2, NCy2, F, OMe, OEt, OiPr, O-] has been synthesized and representative compounds structurally characterized. The reaction of Ru4(CO)13(μ3-PNR2) (1) (R = Cy, iPr) with Ru3(CO)12 in refluxing heptane yields H2Ru3(CO)9(μ3-PNR2) (2) and Ru5(CO)15(μ4-PNR2) (3). An alternative high-yield synthesis for 3 is the reaction of 1 with Ru(CO)5 in refluxing hexane. Treatment of 3 with HBF4·Et2O produces Ru5(CO)15(μ4-PF) (4) in high yield. In contrast, refluxing 3 with HBF4·H2O in CH2Cl2 yields 4 and [R2NH2][Ru5(CO)15(μ 4-PO)] (5), a cluster containing a μ4-phosphorus monoxide (PO) ligand. The reaction of 4 with alcohols affords the series of alkoxy phosphinidene cluster complexes Ru5(CO)15(μ4-POR′) (6) (R′ = Me, Et, iPR). The structures of 2a (R = NCy2), 3a (R = NCy2), 4 (R = F), and the phosphorus monoxide cluster [H2NCy2][Ru5(CO)15(μ 4-PO)] (5a and 6a) (R′ = Me) have been determined by X-ray diffraction studies.
Yamamoto, John H.,Scoles, Ludmila,Udachin, Konstantin A.,Enright, Gary D.,Carty, Arthur J .
p. 84 - 93
(2000)
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Ligand substitutions in Ru-Pt clusters: Isolation of compounds with unusual geometries
Ligand substitution reactions of the COD (1,5-cyclooctadiene) ligand for CO or phosphines in the clusters [Ru5C(CO)14Pt(COD)] (1) and [Ru6C(CO)16Pt(COD)] (2) were investigated. Reactions with carbon monoxide gave selectively [Ru5CPt(CO)16] (3) from 1, but led to loss of either a ruthenium or the Pt(COD) unit from the Ru6Pt cluster (2). Substitution of the COD ligand by PPh3 in 1 gave [Ru5C(CO)14Pt(PPh3)2] (8) selectively, while with dppm the main product of the reaction was [Ru5C(CO)14Pt(μ-dppm)] (10). On the other hand, the reactions involving [Ru6C(CO)16Pt(COD)] (2) and phosphines led mainly to extrusion of the Pt(COD) fragment and formation of Ru-only derivatives. More precisely, with triphenylphosphine, the two clusters [Ru6C(CO)16PPh3] (16) and [Ru6C(CO)15(PPh3)2] (18) were obtained from 2, while with dppm, the compounds [Ru6C(CO)15(dppm)] (15) and [Ru6C(CO)13(dppm)2] (19) were formed. In the latter case, two additional products of increased nuclearity were isolated: [Ru6C(CO)15Pt2(dppm)] (20) and [Ru6C(CO)16Pt3(dppm)2] (21). All the compounds described were characterised by spectroscopic methods and the structures of the new species were determined by X-ray crystallography.
Hermans, Sophie,Khimyak, Tetyana,Feeder, Neil,Teat, Simon J.,Johnson, Brian F.G.
p. 672 - 684
(2003)
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REDUCTION OF CARBON DIOXIDE BY ANIONIC RUTHENIUM CARBONYL CLUSTERS
Carbon dioxide has been found to react with ruthenium carbonyl cluster tetra- and hexa-anions such as K4, Na6, Na4 and Na6 to give carbon monoxide and carbonate by electron transfer from cluster anions.The Ru cl
Chang, Biau-Hung
p. C31 - C33
(1985)
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Reactivity of the 1-azavinylidene cluster [Ru3(μ-H)(μ-N=CPh2)(CO)10] with hydrogen, tertiary silanes and tertiary stannanes
The reactivity of the 1-azavinylidene cluster [Ru3(μ-H)(μ-N=CPh2)(CO)10] (1) with hydrogen, tertiary silanes and tertiary stannanes has been investigated. The reaction of 1 with hydrogen (1 atm, 110°C) gives [Ru4/sub
Bois, Claudette,Cabeza, Javier A.,Franco, R. Jesus,Riera, Victor,Saborit, Enrique
p. 201 - 207
(1998)
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Ligand degradation and phosphorus scavenging in the reaction between 1,2-bis(diphenylphosphino)benzene (dppbz) and Ru6(μ6-C)(CO)17: Synthesis and X-ray structure of the edge-bridged square-pyramidal cluster HRu6(μ5-C)(μ3-P)(CO)14(dppbz)
Thermolysis or Me3NO activation of the hexaruthenium cluster Ru6(μ6-C)(CO)17 in the presence of the diphosphine ligand 1,2-bis(diphenylphosphino)benzene (dppbz) does not furnish the expected dppbz-substituted cluster Ru6(μ6-C)(CO)15(dppbz) but rather HRu6(μ5-C)(μ3-P)(CO)14(dppbz), whose edge-bridged square-pyramidal structure has been established by X-ray crystallography. Accompanying the opening of the original closo Ru6 polyhedron is the dephosphination of a second dppbz ligand through three rapid P-C bond cleavages, leading to the capture of the phosphorus atom as a face-capping phosphido ligand. This unprecedented reactivity between Ru6(μ6-C)(CO)17 and the dppbz ligand is discussed relative to other diphosphine ligands.
Watson, William H.,Kandala, Srikanth,Richmond, Michael G.
p. 1648 - 1652
(2007)
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Catalytic activity of Ru supported on SmCeOx for ammonia decomposition: The effect of Sm doping
SmCeOx composite oxide with Sm3+ occupying Ce4+ site in CeO2 crystal lattice, prepared via citric acid complexation method, was loaded with 2 w% Ru by impregnation method and the as-prepared catalyst was then evaluated for ammonia decomposition. The results show that the partial substitution of Ce4+ by Sm3+ produces a positive effect on the catalyst performance and SmCeOx supported Ru exhibits a much higher low-temperature catalytic activity for ammonia decomposition compared with other supports such as Sm2O3, CeO2, and a physical mixture of Sm2O3 and CeO2. For example, the ammonia conversion is increased from 54.6% to 74.9% at a temperature of 400 ?°C and a space velocity of 3900 ml/gcat·h when CeO2 is replaced by Sm0.4Ce0.6O1.8. TEM and CO chemisorption investigations reveal that the excellent performance of Ru/SmCeOx catalyst is related to its high Ru dispersion. The results of BET, EPR and H2-TPR suggest that the partial substitution of Ce4+ with Sm3+ may induce the formation of oxygen vacancies and the high Ru dispersion can be attributed to the presence of large amount of single-electron trapped oxygen vacancies on the surface of SmCeOx, which have a strong interaction with Ru and thus Ru preferentially occupies the oxygen vacancies. This experimental observation is also supported by the DFT calculation result that Ru species adsorbed on the oxygen vacancy has a low adsorption energy.
Han, Wenfeng,Li, Lichun,Li, Ying,Liu, Zongjian,Tang, Haodong,Wang, Yao,Zhang, Wujian
(2021)
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Reproducible high-yield syntheses of [Ru3(CO)12], [H4Ru4(CO)12], and [Ru6C(CO)16]2- by a convenient two-step methodology involving controlled reduction in ethylene glycol of RuCl3·nH2O
Ru3CO12 [H4Ru4(CO)12], and [Ru6C(CO)16]2- have been synthesized in reproducible high yields and under mild conditions (1 atm) by a two-step methodology involving (i) first carbonylation of RuCl3·nH2O dissolved in ethylene glycol to give a mixture of tri- and di-carbonyl ruthenium(II) species, probably of the kind [Ru(CO)3Cl2(ethylene glycol)] and [Ru(CO)2Cl2(ethylene glycol)x ] (x = 1, 2), and (ii) addition of specific amounts of alkali carbonates and further reductive carbonylation to give the desired ruthenium carbonyl cluster. The selectivity of the second step is controlled by the: (i) nature and quantity of the alkali carbonate (Na2CO3 or K2CO3); (ii) gas-phase composition (CO or CO+H2); (iii) temperature.
Lucenti, Elena,Cariati, Elena,Dragonetti, Claudia,Roberto, Dominique
p. 44 - 47
(2003)
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Trinuclear and tetranuclear iron/ruthenium carbonyl clusters stabilized by bridging selenium ligands
At room temperature, Fe2(CO)6(μ-Se2) reacts with Ru3(CO)12 to form Fe2Ru3(CO)17(μ4-Se)(μ3-Se), and with Ru(CO)4(C2H4) to form Fe2Ru(CO)9(μ3-Se)2. The latter reacts with Fe(CO)5 under visible light irradiation to give Fe3Ru(CO)11(μ4-Se)2, and with Ru(CO)4(C2H4) to form Fe2Ru2(CO)11(μ4-Se)2. Visible light irradiation of a solution containing Fe3(CO)9(μ3-Se)2 and Fe(CO)5 yields Fe4(CO)11(μ4-Se)2. A solution containing Fe3(CO)9(μ3-Se)2 and Ru(CO)4(C2H4) at room temperature with stirring yielded Fe3Ru(CO)11(μ4-Se)2.
Mathur, Pradeep,Hossain, Md. Munkir,Rashid, Raad S.
p. 83 - 86
(1993)
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Synthesis of Indoles by Reductive Cyclization of Nitro Compounds Using Formate Esters as CO Surrogates
Alkyl and aryl formate esters were evaluated as CO sources in the Pd- and Pd/Ru-catalyzed reductive cyclization of 2-nitrostyrenes to give indoles. Whereas the use of alkyl formates requires the presence of a ruthenium catalyst such as Ru3(CO)12, the reaction with phenyl formate can be performed by using a Pd/phenanthroline complex alone. Phenyl formate was found to be the most effective CO source and the desired products were obtained in excellent yields, often higher than those previously reported using pressurized CO. The reaction tolerates many functional groups, including sensitive ones like a free aldehydic group or a pendant pyrrole. Detailed experiments and kinetic studies allow to conclude that the activation of phenyl formate is base-catalyzed and that the metal doesn't play a role in the decarbonylation step. The reactions can be performed in a single thick-walled glass tube with as little as 0.2 mol-% palladium catalyst and even on a 2 g scale. The same protocol can be extended to other nitro compounds, affording different heterocycles.
Ahmed Fouad, Manar,Ferretti, Francesco,Formenti, Dario,Milani, Fabio,Ragaini, Fabio
supporting information
p. 4876 - 4894
(2021/09/20)

The Insertion of Ruthenium into Porphyrins Revisited and Improved: Proof of Concept Results with a Ruthenium(II) Monocarbonyl Compound, and the Spectacular Effect of Propionic Acid
This contribution, that readdresses the insertion of the RuII–CO fragment into model porphyrins (i.e. ruthenation), has a Janus character, with one speculative and one practical side. As a proof of concept we demonstrate that ruthenation of a porphyrin can be performed under relatively mild conditions using the RuII monocarbonyl complex [Ru(CO)(dmso)5][PF6]2 that – besides CO – features exclusively labile dmso ligands. Even though this finding might seem trivial, it is only the second example that uses a RuII carbonyl for porphyrin ruthenation, the first one having been reported almost 50 years ago and then neglected. From a practical point of view, we show the spectacular effect of propionic acid as solvent for performing the ruthenation of neutral and anionic model porphyrins with Ru3(CO)12 (1). This process turned out to be extremely efficient and advantageous in terms of both reaction rates and yields (e.g. 100 % ruthenation of TPP in 30 min at 140 °C) compared to the procedures described in the literature.
Vidal, Alessio,Battistin, Federica,Iengo, Elisabetta,Milani, Barbara,Alessio, Enzo
p. 2883 - 2890
(2019/06/24)

Water-Soluble Ruthenium(II) Carbonyls with 1,3,5-Triaza-7-phosphoadamantane
As a continuation of our strategy for preparing new Ru(II) precursors with improved water solubility through the introduction of highly water-soluble 1,3,5-triaza-7-phosphoadamantane (PTA) supporting ligands in the coordination sphere, in this work, we address the largely unexplored preparation of Ru(II)-PTA carbonyls. Two complementary synthetic approaches were used: (1) the treatment of a series of neutral Ru(II)-CO-dmso compounds of general formula RuCl2(CO)n(dmso)4-n (n = 1-3, 1-5) with PTA; (2) the reaction of Ru(II)-PTA complexes with CO. Through the first approach, we obtained and fully characterized seven novel neutral compounds bearing from one to three PTA ligands per Ru atom, namely, the four monocarbonyls, cis,cis,trans-RuCl2(CO)(dmso-S)(PTA)2 (6), trans-RuCl2(CO)(PTA)3 (7), cis,mer-RuCl2(CO)(PTA)3 (8), and trans,trans,trans-RuCl2(CO)(OH2)(PTA)2 (10), and the three dicarbonyls, trans,trans,trans-RuCl2(CO)2(PTA)2 (11), [RuCl2(CO)2(PTA)]2 (12), and cis,cis,trans-RuCl2(CO)2(PTA)2 (13). The less stable, and thus more elusive, species fac-RuCl2(CO)(PTA)3 (9) and cis,cis,cis-RuCl2(CO)2(PTA)2 (14) were also unambiguously identified but could not be obtained in pure form and fully characterized. The complementary synthetic approach, that involved the treatment of the trans- and cis-RuCl2(PTA)4 (15, 16) isomers with CO, afforded only one new Ru(II)-PTA carbonyl, the cationic species cis-[RuCl(CO)(PTA)4]Cl (17). In general, the choice of the solvent was very relevant for obtaining the products with high yield and purity. We were unable to isolate Ru(II)-PTA compounds with more than two carbonyls. The thermodynamically preferred species have CO trans to Cl and two mutually trans PTAs, and only in the dinuclear compound 12 there is a single PTA per Ru atom. Compounds 7 and 17 feature the unprecedented trans-{Ru(CO)(PTA)} fragment. The X-ray structures of cis,cis,cis-RuCl2(CO)2(dmso)2 (3), 6-8, 10, 11, 13, and 17 are also reported. All compounds are new, are air-stable, and show a good solubility in water (S from 10 to 165 g·L-1) and, most often, also in chloroform.
Battistin, Federica,Balducci, Gabriele,Milani, Barbara,Alessio, Enzo
p. 6991 - 7005
(2018/06/22)

Organoruthenium compound for chemical vapor deposition raw material and production method for the organoruthenium compound
The present invention is an organoruthenium compound for a chemical vapor deposition raw material, including dodecacarbonyl triruthenium represented by the following chemical formula, wherein the iron (Fe) concentration is 1 ppm or less. The DCR in the present invention can be produced by obtaining crude DCR by directly carbonylating ruthenium through allowing a ruthenium salt and carbon monoxide to react with each other and by purifying the crude DCR by a sublimation method. In the synthesis step, the concentration of Fe in the obtained crude DCR is preferably set at 10 ppm or less.
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(2016/04/20)

PRODUCTION METHOD FOR DODECACARBONYL TRIRUTHENIUM
The present invention is a method for producing dodecacarbonyl triruthenium (DCR) including a process of carbonylating ruthenium chloride with carbon monoxide, in which an amine is added to a reaction system at 0.8 molar equivalent or more with respect to chlorine of the ruthenium chloride and the carbonylation is conducted at a reaction temperature of 50 to 100° C. and a reaction pressure of 0.2 to 0.9 MPa. According to the present invention, it is possible to produce dodecacarbonyl triruthenium having less residual impurity metals without applying a reaction condition of a high pressure.
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Paragraph 0031; 0089 - 0097

(2015/12/23)

PURIFICATION METHOD OF DODECACARBONYL TRIRUTHENIUM
PROBLEM TO BE SOLVED: To provide a purification method of dodecacarbonyl triruthenium(DCR) for chemical vapor deposition raw materials which provides DCR suppressed in mixing of impurities in the thin film when a ruthenium thin film is formed. SOLUTION: A purification method comprises purifying an organic ruthenium compound for chemical vapor deposition raw materials consisting of DCR by a recrystallization method under the condition with the concentration of oxygen dissolved in a solvent adjusted to 0.2 mg/L or lower at least in a dissolution stage. The purification method allows separation of minute-amount impurities from DCR, and a ruthenium thin film formed with the obtained DCR suppresses mixing of impurities in the formed film. The purification method is applicable to recovery and purification of DCR after use in the formation of a ruthenium thin film. COPYRIGHT: (C)2016,JPOandINPIT
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Paragraph 0032

(2016/12/26)

Ru0-catalyzed coupling of vinylboronates with silanols, disilanols, and disiloxanediols: A selective route to borasiloxanes
A new highly selective method for the synthesis of borasiloxanes through the O-borylation of silanols, disilanols, and disiloxanediols with vinylboronates in the presence of Ru0 complexes (mainly Ru 3CO12) is described. The method leads to the formation of special compounds with a B-O-Si inorganic framework. When Ru0 complexes are used as a catalyst, no vinylboronate homocoupling is observed. A mechanism for this transformation is proposed on the basis of stoichiometric reactions of Ru0 with triethylsilanol and vinylboronate. A new, selective approach to borasiloxanes through catalytic O-borylation was developed. Vinylboronates are coupled with silanols, silanediols, and siloxanediols, which yield borasiloxanes as the only products with the evolution of ethylene. A mechanism for this Ru3(CO)12-catalyzed transformation is also proposed. Copyright
Fra?ckowiak, Dawid,Walkowiak, J?drzej,Hreczycho, Grzegorz,Marciniec, Bogdan
p. 3216 - 3220
(2014/07/22)

Structures and bonding of η2-bridging co ligands and their influence on the structures and rearrangements of higher nuclearity metal carbonyl cluster complexes
Three products were obtained from the reaction of IrRu3(CO) 13(μ3-H) with P(But)3 in a hexane solution at reflux for 30 min. These have been identified as IrRu 3(CO)12[P(But)3](μ-H) (1; 15% yield), IrRu2(CO)9[P(But)3](μ-H) (2; 29% yield), and IrRu3(CO)10(μ3- η2-CO)[P(But)3]2(μ-H) (3; 19% yield). Compound 1 is simply a P(But)3 derivative of IrRu3(CO)13(μ3-H). Compound 2 is electronically unsaturated and has a vacant coordination site located on the iridium atom. Compound 3 contains a butterfly tetrahedral cluster of four metal atoms with a rare η2 triply bridging CO ligand. Compound 3 reacts with Ru(CO)5 to yield the higher nuclearity cluster complex IrRu4(CO)12(μ4-η2-CO) [P(But)3]2(μ3-H) (4), which contains five metal atoms arranged in the form of an iridium-capped butterfly tetrahedron of four ruthenium atoms. Compound 4 contains a η2- quadruply bridging CO ligand. Compound 4 reacts with CO to yield the compound IrRu4(CO)14P(But)3(μ4- η2-CO)(μ-H), 5 which contains five metal atoms in the form of a spiked-tetrahedron. Compound 5 also contains a η2 quadruply bridging CO ligand. Compound 5 was converted to 2 in 36% yield by removal of two of the Ru groups by treatment with CO at 70 C/10 atm. All of the new products were characterized structurally by single-crystal X-ray diffraction analyses. The η2-coordinated bridging CO ligands serve as four-electron donors. The nature of the bonding of the different types of η2- bridging CO ligands to the metal atoms in these clusters was investigated by DFT computational methods.
Adams, Richard D.,Zhang, Qiang
p. 5171 - 5179
(2013/10/08)

Reactions of unsymmetrically substituted N-heterocyclic carbenes with Ru3(CO)12
Reactions of a series of unsymmetrically substituted N-heterocyclic carbene ligands with Ru3(CO)12 afforded a variety of mononuclear (1, 2), trinuclear (3, 4, 5, and 5'), and tetranuclear (6, 7) ruthenium complexes via intramolecular ruthenium-mediated sp2 and sp 3 C-H bond activations. Complexes 6 and 7 include an octahedral cluster skeleton consisting of four ruthenium atoms and two metalated carbon atoms. The formation of this type of ruthenium clusters is proposed to involve the initial C-C double-bond migration and subsequent sp2 C-H bond activations. All new complexes were fully characterized, and the molecular structures of 1, 2, 5, 6, and 7 were determined by X-ray diffraction analysis.
Zhang, Congying,Li, Bin,Song, Haibin,Xu, Shansheng,Wang, Baiquan
p. 3029 - 3036
(2011/07/08)

Reactivity of cationic triruthenium carbonyl clusters: From pyrimidinium ligands to N-heterocyclic carbenes
The reaction of [Ru3(CO)12] with pyrimidine (Hpym) leads to the isomeric cyclometalated derivatives [Ru3(μ-H)(μ- κ2N1,C6-pym)(CO)10] (1) and [Ru3(μ-H)(μ-κ2N1,C 2-pym)(CO)10] (2), which have been treated with [Me 3O][BF4] to give the corresponding N-methylpyrimidinium derivatives [Ru3(μ-H)(μ-κ2N1,C 6-pymMe)(CO)10][BF4] (3[BF4]) and [Ru3(μ-H)(μ-κ2N1,C 2-pymMe)(CO)10][BF4] (4[BF4]). The reaction of 4[BF4] with K-Selectride renders a separable mixture of two neutral trinuclear products, [Ru3(μ-H){μ- κ2N1,C2-(6-HpymMe)}(CO)9] (5) and [Ru3(μ-H){μ-κ2N1,C 2-(4-HpymMe)}(CO)9] (6), which arise from the nucleophilic attack of a hydride at the ligand C6 and C4 carbon atoms of 4+. This cationic complex can be reduced to the short-lived radical species 4?, which spontaneously dimerizes by forming an intermolecular C-C bond between the ligands of two such radicals. Three hexanuclear derivatives, [Ru6(μ-H)2{μ6- κ4N1,N1′,C2,C 2′-(4,6′-bipymMe2)}(CO)18] (isomers 7 and 8) and [Ru6(μ-H)2{μ6- κ4N1,N1′,C2,C 2′-(4,4′-bipymMe2)}(CO)18] (isomer 9), have been isolated by reducing 4[BF4] with cobaltocene. Molecular orbital calculations (at the DFT level) and electrochemical studies have helped rationalize the experimental results. The ligand-based character of the LUMO of 4+ and its atomic orbital composition account for the regiochemistry observed in the reactions of this cationic complex. The N-heterocyclic ligands of 5-9, which have two N atoms in a six-membered ring and a doubly metalated N atom, constitute novel types of N-heterocyclic carbenes.
Cabeza, Javier A.,Del Rio, Ignacio,Perez-Carreno, Enrique,Pruneda, Vanessa
p. 1148 - 1156
(2011/04/22)

Photochemical synthesis of ruthenium-carbonyl compounds with thioether ligands and subsequent oxidative cleavage of trinuclear complexes by chlorinated solvents
The photochemical reaction of [Ru3(CO)12] with thioether ligands in THF leads to the isolation of tetranuclear ruthenium-carbonyl cluster compounds of the formula [Ru4(CO) 13(μ2-R2S)]. In these compounds, ruthenium atoms adopt a typical butterfly arrangement. If chelating ligands with two thioether functions are introduced, the reaction leads to mixtures of the trinuclear substitution products [Ru3(CO)10(RSSR)] and [Ru3(CO)8(RSSR)2]. The latter may be oxidatively cleaved by the use of chlorinated solvents to produce the mononuclear compound [Ru(CO)2Cl2(RSSR)] or the dinuclear complex [Ru2(CO)2(μ2-Cl)2Cl 2(RSSR)2] depending on the reaction conditions. Five new ruthenium-carbonyl-thioether complexes were characterized by X-ray diffraction. Irradiation of [Ru3(CO)12] in THF in the presence of thioether ligands yields ruthenium-carbonyl compounds [Ru4(CO) 13(μ2-R2S)] in the case of monodentate ligands, but [Ru3(CO)10(RSSR)] and [Ru3(CO) 8(RSSR)2] if bidentate thioether ligands are used. The latter may be oxidatively cleaved by CHCl3 to produce the dinuclear complex [Ru2(CO)2(μ2-Cl)2Cl 2(RSSR)2]. Copyright
Maiti, Biplab K.,Goerls, Helmar,Klobes, Olaf,Imhof, Wolfgang
p. 1545 - 1552
(2011/06/22)

Preparation of ruthenium and osmium carbonyl complexes using microwave heating: demonstrating the use of a gas-loading accessory and real-time reaction monitoring by means of a digital camera
By using a gas-loading accessory, we show that it is possible to perform reactions involving gases and prepare organometallic complexes easily in good yields using microwave heating. The complexes Ru3(CO)12, H4Ru4(CO)12, and H2Os 3(CO)10 are prepared. Ligand substitution reactions of Ru3(CO)12 are also studied and, in the case of the reaction with triphenylphosphine, the reaction is monitored in real time by means of a digital camera interfaced with the microwave unit.
Leadbeater, Nicholas E.,Shoemaker, Krista M.
p. 1254 - 1258
(2009/01/30)

Surface-assisted synthesis and behavior of dimetallic mixed-metal complexes [M2Cl2(μ-Cl)4(CO)6M′(L) 2] (M = Ru, Os; M′ = Fe, Co; L = CH3CH 2OH, H2O)
The reductive carbonylation of ruthenium and osmium halides in the presence of cobalt and iron surfaces was studied. In these surface-assisted reactions the metal surface plays an active role in releasing metal ions, which can be used for the in situ synthesis of mixed-metal compounds. A linear, dimetallic, chlorido-bridged, trinuclear complex [Ru2Cl2(μ-Cl) 4(CO)6Co(CH3CH2OH)2] was obtained by the interaction between reducing RuCl3 and the cobalt surface. In the reaction the RuCl3 is reduced with carbon monoxide in the presence of a solid cobalt surface in ethanol solution. During the reduction of the RuCl3 the cobalt surface was simultaneously corroded, releasing cobalt cations. In addition to [Ru2Cl 2(μ-Cl)4(CO)6Co(CH3CH 2OH)2], the reaction also produced other trinuclear complexes and mononuclear products, such as a bent and linear dimetallic, chlorido-bridged complex with the aqua ligand [Ru2Cl 2(u-Cl)4(CO)6Co(H2O)2] and ionic [RuCl3(CO)3]2[Co(H2O) 6], The carbon monoxide reduction of Rul3 produced the ionic complex [RuI3(CO)3]2[M′(H 2O)6] (M′ = Fe, Co) in the presence of iron, stainless steel or cobalt. Iodido-bridged trinuclear mixed-metal complexes were not observed. The surface-assisted process proved to be useful with other metal combinations as well. When RuCl3 was replaced with OsCl3, a variety of trinuclear mixed-metal complexes, such as [Os2Cl 2(u-Cl)4(CO)6Co(CH3CH 2OH)2] and ionic [OsCl3(CO)3] 2[M(H2O)6] (M = Fe, Co), were obtained, depending on the metal surface used. Due the lability of the chlorido-bridged trinuclear complexes, the possible decomposition steps of [M2Cl 2(μ-Cl)4(CO)6M′(CH3CH 2OH)2] (M = Ru, Os; M′ = CO, Fe) were studied computationally, using DFT methods. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
Jakonen, Minna,Hirva, Pipsa,Nivajaervi, Taina,Kallinen, Mirja,Haukka, Matti
p. 3497 - 3508
(2008/03/13)

The subtle effects of iron-containing metal surfaces on the reductive carbonylation of RuCl3
The use of iron-containing metal surfaces, Fe, Fe-Cr-alloy and stainless steel, for the synthesis of mixed metal Ru-Fe compounds has been studied. The studied process was reductive carbonylation of RuCl3 in the presence of a metal surface. Reactions were carried out in ethanol solutions under 10-50 bar carbon monoxide pressure at 125 °C using an autoclave. During the reaction the metal surface was oxidized, releasing iron into the solution and acting as a sacrificial source of iron. Under these conditions the corrosion of the metal surface was facile and produced a series of iron-containing species. In addition to the formation of most obvious iron(ii) products, such as [Fe(H2O)6]2+ or [FeCl2(H 2O)4] the use of the metal surface also provided a route to novel labile trinuclear [Ru2Cl2(-Cl) 4(CO)6FeL2] (L = H2O, EtOH) complexes. The stability and reactivity of the [Ru2Cl 2(-Cl)4(CO)6FeL2] complexes were further studied using computational DFT methods. Based on the computational results a reaction route has been suggested for the formation and decomposition of [Ru2Cl2(-Cl)4(CO)6FeL 2]. The Royal Society of Chemistry 2006.
Haukka, Matti,Jakonen, Minna,Nivajaervi, Taina,Kallinen, Mirja
p. 3212 - 3220
(2007/10/03)

Ligand displacement reaction of Ru(η4-1,5-COD)(η6-1,3,5-COT) with Lewis bases
Reactions of Ru(η4-1,5-COD)(η6-1,3,5-COT) (1) (COD = cyclooctadiene, C8H12; COT = cyclooctatriene, C8H10) with a series of Lewis bases are studied. Treatments of 1 with P(OMe)3, P(OEt)3, P(OMe)2Ph, P(OEt)2Ph, P(OiPr)3, P(OMe)Ph2, or P(OEt)Ph2 lead to the formation of Ru(η4-1,5-COD)(η4-1,3,5-COT)L (2) followed by preferential liberation of the 1,5-COD ligand to give COT complexes formulated as Ru(6-η1:1-3-η3-COT)L3 (3) and Ru(η4-1,3,5-COT)L3 (4). Reaction of 1 with P(OPh)3 also gives 2, but further treatment of this system leads to the liberation of both 1,5-COD and 1,3,5-COT to give a mixture of Ru(η4-1,5-COD)L3 (5) and Ru(6-η1:1-3-η3-COT)L3 (3) and finally gives Ru{P(OC6H4)(OPh)2}2- {P(OPh)3}2 (6h). In the reaction of 1 with tert-butylisonitrile, 1,3,5-COT is initially liberated with concomitant formation of Ru(η4-1,5-COD)(CNtBu)3 (5j), which further reacts with the liberated 1,3,5-COT, giving eventually Ru(6-η1:1-3-η3-COT)(CNtBu)3 (3j). The molecular structure of 5j determined by X-ray structure analysis reveals that one of the isonitrile ligands has a considerable carbene character. In the presence of excess isonitrile, the homoleptic complex Ru(CNtBu)5 (7) is formed. On the other hand, 1 does not react with poor π-accepting ligands such as NEt3, pyridine, and (dimethylamino)pyridine as well as bulky phosphorus ligands such as triphenylphosphine and tricyclohexylphosphine. These results suggest that the initial coordination of electron-donating ligands to Ru essentially encourages the dissociation of the 1,5-COD ligand, but the π-accepting ability of the ligand induces the dissociation of the 1,3,5-COT ligand.
Hirano, Masafumi,Asakawa, Rie,Nagata, Chifumi,Miyasaka, Takashi,Komine, Nobuyuki,Komiya, Sanshiro
p. 2378 - 2386
(2008/10/08)

Di- and Trinuclear Ruthenium and Osmium Bis(2-pyridyl) Ketone Oximate Derivatives
Treatment of [Ru3(CO)12] with bis(2-pyridyl) ketone oxime (Hdpko) in refluxing THF leads to a separable mixture of [Ru 3(μ,η3-dpko-N, N,O)2(CO)8] (1) and [Ru2(μ,η3-dpko-N,N,O)2(CO) 4] (2). In both complexes, two Ru atoms are doubly bridged by two dpko ligands, which are attached to a Ru atom through the oximate O atom while chelating the other Ru atom through the N atoms of a pyridyl group and the oximate fragment. While the Ru-Ru distance of the bridged edge of complex 1 is very long [3.5388(9) A], that of complex 2 is very short [2.620(1) A]. The acetonitrile complexes [M3(CO)10(MeCN) 2] (M = Ru, Os) react with Hdpko in THF at room temperature to give [M3(μ-H)(μ,η3-dpko-N,N,O)(CO)9] [M = Ru (3) Os (4)], in which the dpko ligand behaves in the same way as in 1 and 2. The thermal reaction of 3 with Hdpko leads to a mixture of 1 and 2, while an analogous treatment of complex 4 gives [Os3(μ,η 3-dpko-N,N,O)2(CO)8] (5), which is isostructural with complex 1. Compounds 1 and 3 are the first examples of ruthenium clusters containing oximate ligands. These oximate complexes display low activity as DNA cleavage agents, requiring high complex concentrations, long incubation times, and the use of UV light as a trigger. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.
Cabeza, Javier A.,Del Rio, Ignacio,Riera, Victor,Suarez, Marta,Alvarez-Rua, Carmen,Garcia-Granda, Santiago,Chuang, Shih Hsien,Hwu, Jih Ru
p. 4159 - 4165
(2007/10/03)

First direct observation of a CO-bridged primary photoproduct of [Ru3(CO)12] by picosecond time-resolved IR spectroscopy
For the first time, a CO-bridged primary photoproduct was observed for [Ru3(CO)12] by using picosecond time-resolved IR spectroscopy (ps-TRIR).
Vergeer, Frank W.,Hartl, Frantisek,Matousek, Pavel,Stufkens, Derk J.,Towrie, Michael
p. 1220 - 1221
(2007/10/03)

Polyether phosphite for hydroformylation of higher olefins in non-aqueous system and catalyst recovery
A new rhodium catalyst recyling system for non-aqueous hydroformylation of 1-decene is described using a polyether phosphite, OPGPP with a polyether chain of over 19 ethylene glycol units. The corresponding rhodium complexes formed in situ are active for non-aqueous hydroformylation of 1-decene. The catalysts precipitated from the reaction mixture on cooling to room temperature or lower and were reused up to six times without obvious decrease in activity. P loss in the seventh reaction run was detected to be 0.92%. Complex OPGPP/Ru3(CO)3 formed in situ has also been proved to be a moderate catalyst for the non-aqueous hydroformylation of 1-decene. The catalysts retained considerable activity up to 87.1% after four successive reaction runs.
Liu, Xiaozhong,Li, Hongmei,Wang, Yanhua,Jin, Zilin
p. 83 - 90
(2007/10/03)

Ruthenium cluster carbonyls containing ligands derived from ferrocenylalkynes
Reactions of FcC≡CH (a), HC≡CC≡CFc (b) and FcC≡CC≡CFc (c) with Ru3(CO)10(NCMe)2 (all) and Ru3(μ-dppm)(CO)10 (b and c only) are described. Among the products, the complexes CFc)21(μ-dppm)(μ-CO)(CO)5 7 were characterised, including single-crystal structure determinations for 1.3.5 and 7; that of 7 did not differ significantly from an earlier study of a mixed CH2Cl2-C6H6 solvate. 2002 Elsevier Science B.V. All rights reserved.
Bruce, Michael I.,Skelton, Brian W.,White, Allan H.,Zaitseva, Natasha N.
p. 188 - 197
(2007/10/03)

The clusters HRu3W(η5-Cp)(CO)11-x(PPh3) xBH (x = 1, 2): Preparations, characterizations and the crystal structure of HRu3W(η5-Cp)(CO)10(PPh3)BH
The clusters HRu3W(η5-Cp)(CO)11-x(PPh3) xBH (x = 1, 2) have been prepared by reaction of PPh3 with HRu3 W(η5-Cp)(CO)11BH after Me3NO-MeCN-activat
Housecroft, Catherine E.,Nixon, Dorn M.,Rheingold, Arnold L.
p. 89 - 94
(2007/10/03)

Preparation and structural characterisation of some ruthenium cluster carbonyls containing allenylidene ligands
The chemistry of some ruthenium cluster carbonyls containing allenylidene ligands has been reinvestigated. Treatment of Ru3(u-H){u3-C2CAr2(OH)}(CO)9 [Ar = Ph 15, toi (toi = 4-MeC6H4)] with HBF4-OMe2 gave Ru3(u-H)(u3-CCCAr2)(CO)9 (Ar = Ph, R = H, Me; Ar =
Bruce, Michael I.,Skelton, Brian W.,White, Allan H.,Zaitseva, Natasha N.
p. 881 - 890
(2007/10/03)

Reactions of a transient carbonyl(chloro)(hydrido)ruthenium(II) complex with ethylene, alkynes, and CO; chemistry of the new anion [Ru2(CO)4Cl5]-
A 97% yield of [Ru3(CO)12] (2) in 20 minutes is obtained simply by treating [Ru(CO)3Cl2(thf)] with KOH under CO (1 atm). The reduction to Ru0 can be explained in terms of the facile reductive elimination of HCl from the transient hydrido complex 1. Though elusive, the latter can be intercepted by olefins or alkynes to produce trappable alkyl or alkenyl complexes.
Faure, Matthieu,Maurette, Luc,Donnadieu, Bruno,Lavigne, Guy
p. 518 - 522
(2007/10/03)

High-yield syntheses, under mild conditions, of various neutral and anionic ruthenium and osmium carbonyl clusters by controlled reduction in ethylene glycol of [M(CO)3Cl2]2 or MCl3 (M=Ru, Os) in the presence of
[M3(CO)12], [H4M4(CO)12], [H3M4(CO)12]- (M=Ru, Os) and [Ru6C(CO)16]2- have been synthesized in high yields by one-pot contr
Roveda, Carmen,Cariati, Elena,Lucenti, Elena,Roberto, Dominique
p. 117 - 127
(2007/10/03)

A practical synthetic method for dodecacarbonyltrimthenium, Ru3(CO)12, using ruthenium dioxide hydrate
Ruthenium dioxide hydrate (RuO2·xH2O) reacts with carbon monoxide at 5-20 atm to give dodecacarbonyltriruthenium, Ru3(CO)12, in an excellent yield. Ruthenium carboxylate complexes [Ru2(OCOR)2(CO)4]n (R = H or CH3) are almost quantitatively obtainable from the same reaction in the presence of formic or acetic acid. These isolable Ru complexes and the Ru dioxide hydrate efficiently effect a reductive carbonylation of nitrobenzene in aniline to produce N,N′-diphenylurea.
Shimoyama, Izumi,Hachiya, Tetsuo,Mizuguchi, Masatsugu,Nakamura, Tomomichi,Kaihara, Mikio,Ikariya, Takao
p. 197 - 199
(2007/10/03)

Reactions of Ru3(CO)10(NCMe)2 with ethyne: Molecular structures of some prototypical cluster complexes
Formation of Ru4, Ru5 and Ru6 complexes accompanies the synthesis of the previously described of Ru3(μ3-C2H2)-(μ-CO)(CO) 9 1 [from Ru3(CO)10(NCMe)2 and C2H2] and its conversion to Ru3(μ-H)(μ3-C2H)(CO)9 2. In Ru4(μ4-C2H2)-(CO)12 4, the ethyne forms part of the pseudo-octahedral C2Ru4. In contrast, μ4-η2-CCH2 ligands are found in Ru5(μ4-CCH2)(CO)15 5 and Ru6(μ4-CCH2)2(CO)16 7; in the former, the Ru5 core is an edge-bridged tetrahedron, while in 7, two butterflies share an Ru=Ru double bond [2.686(1) A]. Other minor products are Ru5(μ-CHCHCCH2)-(CO)15 6 and Ru6(μ-H)(μ4-C)(μ-CCMe)(μ-CO)(CO)16 8. Crystal structures of 1, 2,4, 5 and 7·CH2Cl2 are reported.
Bruce, Michael I.,Skelton, Brian W.,White, Allan H.,Zaitseva, Natasha N.
p. 1445 - 1453
(2007/10/03)

Oxide bridged mixed metal organometallics: The reaction of Ru4(CO)13[μ3-PN(R)2] R = iPr, Cy with Cp*W(O)2CCPh
The reaction of the tungsten oxo acetylide complex Cp*W(O)2CCPh with Ru4(CO)12-13[μ3-PN(R)2] where R = iPr or Cy affords two oxo bridged metal clusters η5-Cp*W(μ-O)Ru4(CO) 9(μ-CO)[μ3-η2-P(O)N(R) 2](μ4-η2-CCPh) (2) and η5-Cp*W(μ-O)2Ru4(CO) 10[μ3-PN(R)2](μ4-η 2-CCPh) (3). X-ray analysis shows that 2 has a single W-O-Ru oxide bridge and contains the first example of a diisopropylaminophosphinidoxo ligand while in 3 both oxide ligands bridge W-Ru bonds. The reaction of 3 with HBF4 · Et2O forms the new W-F complex η5-Cp*WF(μ3-O)HRu4(CO) 9[μ3-η2-P(O)N(R)2](μ 4-η2-CCPh) (4).
Yamamoto, John H.,Enright, Gary D.,Carty, Arthur J.
p. 126 - 133
(2007/10/03)

Synthesis, structural characterisation and electrochemistry of ruthenium carbonyl clusters derived from ferrocenyl(formyl)acetylene
Two new ferrocenyl ruthenium carbonyl clusters, [Ru4(CO)12(μ4-η1,η 1,η2,η2-{(C5H 5)Fe(C5H4CCCHO)})] 1 (20%) and [Ru3(CO)8(μ3-η1,η 2,η4-{(C5H5)Fe(C 5H4CCCHO)}2)] 2 (10%), have been synthesised by reaction of (C5H5)Fe(C5H4C≡CCHO) with triruthenium dodecacarbonyl in cyclohexane under refluxing conditions. Thermolysis of 1 in refluxing toluene led to the formation of [Ru5(CO)13(μ-H)(μ5-C)(μ 2-η1,η1-{(C5H 5)Fe(C5H4C)})] 3 (10%). Reaction of [Ru3(CO)10(NCMe)2] with ferrocenyl(formyl)acetylene afforded the triruthenium cluster [Ru3(CO)9(μ-CO)(μ3-η 1,η1,η2-{(C5H 5)Fe(C5H4CCCHO)})] 4 (30%). All these new compounds have been characterised fully by conventional spectroscopic and X-ray diffraction methods. The structure of 1 consists of a ferrocenyl carboxaldehyde bound to the Ru4 butterfly skeleton via a typical μ4-η1, η1, η2, η2 coordination mode. Cluster 2 is based upon an Ru3 closed triangle bearing a metallacyclopentadiene ring that arises from the coupling of two ligand molecules with the formation of O→Ru dative bond. Thermolysis of 1 afforded a rare pentanuclear ruthenium cluster containing a carboferrocenyl fragment with a μ2-η1,η1 mode. Both fluxional and electrochemical behaviour of cluster 3 have been studied. Compound 4 consists of an alkyne ligand bound to the triruthenium cluster unit via a typical μ3-(η2-) coordination mode.
Lau, Cindy Sze-Wai,Wong, Wing-Tak
p. 113 - 124
(2007/10/03)

(Carbonyl)iron-selenolates: New synthetic methods and reactions with electrophiles. Crystal structures of [(CO)6Fe2(μ-SeR)2]; R = Me3SiCH2 and p-O2NC6H4CH2, {(CO)6Fe2[μ-η2-Se,Se′-o-(SeCH2C6H4CH2Se)]}
The reactions of Fe(CO)5 or Fe3(CO)12 with NaBEt3H or KB[CH(CH3)C2H5]3H, respectively and treatment of the resulting carbonylates M2Fe(CO)4, M = Na, K with elemental selenium in appropriate ratios lead to the formation of M2[Fe2(CO)6(μ-Se)2]. Subsequent reactions with organo halides or the complex fragment cpFe(CO)2+, cp = η5-C5H5 afforded the selenolato complexes [Fe2(CO)6(μ-SeR)2], R = CH2SiMe3 (1), CH2Ph (2), p-CH2C6H4NO2 (3), o-CH2C6H4CH2 (4) and cpFe(CO)2+ (5) in moderate to good yields. A similar reaction employing Ru3(CO)12, Se and p-O2NC6H4CH2Br leads to the formation of the corresponding organic diselenide. The X-ray structures of 1, 3, 4 and 5 were determined and revealed butterfly structures of the Fe2Se2 cores. The substituents in 1, 3 and 5 adopt different conformations depending on their steric demand. In 4, the conformation is fixed because of the chelate effect of the ligand. The Fe-Se bond lengths lie in the range 235 to 240 pm, with corresponding Fe-Fe bond lengths of 254 to 256 pm. The 77Se NMR data of the new complexes are discussed and compared with the corresponding data of related complexes.
Jaeger, Stefan,Jones, Peter G.,Laube, Joerg,Thoene, Carsten
p. 352 - 358
(2008/10/08)

The reactivity of (μ-H)2Ru3(CO)9(μ3-η2-C8H12) and (μ-H)Ru3 (Co)9 (μ3-η3-C12 H19)
The reactivity of (μ-H)2Ru3(CO)9(μ3-η2-C8H12) (1) and (μ-H)Ru3(CO)9(μ3-η3-C12H19) (2) with hydrogen and carbon monoxide was studied at elevated temperatures. Also the catalytic activity of 1 in homogeneous hydrogenation of 1-hexene was studied. At the lower carbon monoxide pressures compounds 1 and 2 converted to Ru3(CO)12 while at higher pressures they tend to fragmentate to the other ruthenium carbonyl compounds. Under a hydrogen atmosphere 1 and 2 converted to H4Ru4(CO)12 and at higher pressures tend to fragmentate to insoluble black precipitate. Complex 1 has a moderate activity in homogeneous hydrogenation of 1-hexene. Its activity is dependent on the temperature: activity increases when the temperature goes up.
Kallinen,Pakkanen,Pakkanen
p. 233 - 239
(2008/10/09)

Synthesis, characterization, crystal structures and reactivity of a series of ruthenium nitrene and nitrido carbonyl clusters containing bridging alkyne ligands
The reactions of [Ru3(CO)9(μ3-CO)(μ3-NOMe)] 1 with alkynes, PhC2R, in n-hexane afforded the new cluster [Ru3(CO)9(μ3-NOMe)(μ 3-η2-RC2Ph)] (2a, R = H; 2b, R = Ph) in high yields. The molecules consist of an open triangular core of three metal atoms with triply bridging alkyne and μ3-NOMe ligands on opposite sides of the cluster. Upon thermolysis in n-octane, [Ru4(CO)9(μ-CO)2(μ 4-NOMe)(μ4-η2-HC2Ph)] 3a, [Ru4(CO)9(μ-CO)2-{μ 4-NC(O)OMe}(μ4-η2-HC2Ph)] 4a and [Ru5(CO)13(μ-CO)(μ4-NH)(μ 4-η2-HC2Ph)] 5a were isolated from 2a, while [Ru4(CO)9(μ-CO)2(μ 4-NOMe)(μ4-η2-PhC2Ph)] 3b, [Ru4(CO)9(μ-CO)2{μ 4-NC(O)OMe}(μ4-η2-PhC2Ph)] 4b, [Ru4(CO)9(μ-CO)2(μ 4-NH)(μ4-η2-PhC2Ph)] 6b and [Ru6(CO)13(μ-H)(μ5-N)(μ 3-η2-PhC2Ph)2] 7b were obtained from 2b. The structures of 3a, 3b, 4a and 4b consist of a slightly twisted square base of four metal atoms with quadruply bridging alkyne and μ4-NOMe or μ4-NC(O)OMe ligands on opposite sides of the clusters. Cluster 5a has a structure analogous to that of 3a with quadruply bridging phenylacetylene and μ4-nitrene (NH) ligands but differs from 3a due to the presence of a Ru(CO)4 group on one edge of the tetraruthenium cluster, whilst cluster 7b contains six ruthenium atoms and a μ5-N nitrido atom. Five ruthenium atoms out of the six arrange in a novel wingtip-bridged metal skeleton. The binuclear metallapyrrolidone complex [Ru2(CO)6{μ-η3-HC 2(Ph)C(O)N(OMe)}] 8a was isolated from the direct reaction of 1 and phenylacetylene in refluxing n-octane, in which interaction of phenylacetylene with CO and the NOMe nitrene moiety was observed. Complex 3a converts into 4a in refluxing n-octane with or without bubbling CO. Substitution of MeCN with 3a led to the activated [Ru4(CO)8(μ-CO)2(NCMe)(μ 4-NOMe)-(μ4-η2-HC2Ph)] 9a in moderate yields. Monosubstituted [Ru4(CO)8(μ-CO)2(PPh3)(μ 4-NOMe)(μ4-η2-HC2Ph)] 10a was isolated stoichiometrically when 9a was stirred with PPh3. However, direct substitution on 3a with PPh3 in the presence of Me3NO gives disubstituted [Ru4(CO)7(μ-CO)2(PPh3) 2(μ4-NOMe)(μ4-η2-HC 2Ph)] 11a in addition to 10a. Nucleophilic attack of H- takes place on 3a and 4a and of I- on 3a, a terminal carbonyl ligand is replaced by these anionic ligands and the products were characterized by negative ionization fast atom bombardment mass spectrometry.
Ho, Emmie Ngai-Man,Wong, Wing-Tak
p. 4215 - 4228
(2007/10/03)

Carbon-Hydrogen Bond Activation by Triruthenium Carbonyl Species during Carbon Monoxide Promoted Elimination of 4,5-Dihydroacenaphthylene from [(μ2: η1: η5-C12H10)Ru3H 2(CO)7]: Implication of Reaction Intermediates
Oxidative addition of a vinylic C-H bond occurred during the CO-promoted elimination of 4,5-dihydroacenaphthylene (3) from [(μ2 : η1 : η5-C12H10)Ru3H 2(CO)7] (2) in CH2Cl2. The product, [(μ3 : η1 : η2 : η2-C12H9)Ru3H(CO)9] (4), was isolated and characterized by spectroscopy and crystallography. The carbonylation of a deuterium-labelled complex, [(μ2 : η1 : η5-C12H8D2)Ru3D 2(CO)7] (2-d4), under the same conditions as that from 2 to 3 in CH2Cl2 afforded 4,5-dideuterioacenaphthylene (3-d2) and [(μ3 : η1 : η2 : η2-C12H7D2)Ru 3H(CO)9] (4-d2). The lack of incorporation of deuterium atoms into the ruthenium hydride in 4-d2 suggested that dissociation of D2 from the triruthenium moiety in 2-d4 induced the oxidative addition of the vinylic C-H bond. Further carbonylation of 4 did not occur under the same conditions as the reaction from 2 to 4, but gave 3 in moderate yields under higher CO pressure (8 atm) at 50 - 100 °C. These results suggest that 4 was not directly involved in the CO promoted elimination of 3 from 2, but was closely related to the actual intermediates. Possible reaction mechanisms are discussed.
Nagashima, Hideo,Suzuki, Akihiro,Nobata, Mitsuharu,Aoki, Katsuyuki,Itoh, Kenji
p. 2231 - 2237
(2007/10/03)

The synthesis of novel neutral mononuclear ruthenium fragments for cluster capping reactions and their reactivity
The mononuclear complex [Ru(CO)4(C2H4)] (1) reacts with bidentate phosphines to yield the corresponding [Ru(CO)4(η1-bidentate phosphine)] (3) complex in quantitative yield thereby offering a new route to this class of compound. Broadband UV photolysis of dichloromethane solutions of the 1,2-bis(diphenylphosphino)propane (dppp) complex [Ru(CO)4(η1-dppp)] (3d) under an atmosphere of ethene yields the di-substituted complex [Ru(CO)3(η1-dppp)(η2-C2H4)] (9d) in quantitative yield. Both 3d and 9d show potential in selective cluster capping reactions as illustrated by their reactivity with [Ru5C(CO)15] (4) and [Ru3(CO)12] (2).
Leadbeater, Nicholas E.,Lewis, Jack,Raithby, Paul R.,Edwards, Andrew J.
p. 567 - 572
(2007/10/03)

Synthesis, characterization and crystal structures of a series of ruthenium μ4-nitrene carbonyl clusters
Methylation of [Ru3(CO)10(NO)]- anion has led to the isolation of [Ru6(μ-H)(CO)16(μ-CO)(μ4-NH){μ 3-η2-C(O)OMe}] 1 in addition to the major product [Ru3(CO)10(NOMe)] 2. Hydrogenation of 2 in refluxing hexane gave [Ru3(μ-H)2(CO)9(NH)] 3 and [Ru3(μ-H)2(CO)9(NOMe)] 4 in moderate yields, but in the presence of [Ru3(CO)12] it gave [Ru6(μ-H)(CO)16(μ-CO)2(μ 4-NH)(μ-OMe);] 5 and [Ru5(μ-H)3(CO)13(μ 4-NH)(μ3-OMe)] 6 in addition. Thermolysis of 2 in toluene at 90°C for 3 h yielded [Ru4(CO)12(μ4-N)(μ-OMe)] 7 and [Ru6(CO)16(μ-CO)2(μ 4-NH)(μ-OMe)2] 8. Pyrolysis of 4 at 140°C for 2 h afforded [Ru6(CO)15(μ-CO)2(μ 4-NH)(μ-OMe){μ3-η2-N(H)C(O)OMe}] 9, [Ru6(μ-H)2(CO)14(μ-CO) 2{μ5-η2-NC(O)OMe}] 10 and [Ru6(CO)16(μ-CO)2(μ 4-NH)(μ-OMe)(μ-NCO)] 11 together with the known clusters [Ru4H2(CO)13] and [Ru3(μ-H)(CO)10(NH2)]. The crystal structures of 1 and 3-11 have been determined. Clusters 1, 5, 6, 8, 9 and 11 consist of a square-pyramidal 'Ru4(CO)8(μ4-NH)' moiety with four ruthenium atoms forming a square-planar base which is capped by a quadruply bridging nitrene ligand. For 1, 5, 8, 9 and 11, two additional ruthenium fragments bridge the opposite edges of the Ru4(CO)8(μ4-NH) metal core to give 'boat' form hexaruthenium nitrene compounds. Compound 6 also has a Ru4(CO)8(μ4-NH) moiety, but with only one bridging Ru(CO)4 fragment at one of the Ru-Ru edges of the tetraruthenium plane while the remaining three are bridged by hydrides. Compound 10 comprises a square-pyramidal array of five ruthenium atoms with a Ru(CO)3 unit bridging one of the Ru-Ru edges of the base. The other side of the square plane is quadruply capped by the nitrogen atom of a NC(O)OMe ligand with the oxygen atom of the acyl group bonded to the apical Ru(CO)3 unit. Compound 7 possesses a butterfly arrangement of four Ru atoms with the methoxy group bridging the hinge.
Lee, Kenneth Ka Hong,Wong, Wing Tak
p. 1707 - 1720
(2007/10/03)

Benzynechromium tricarbonyl. Further synthetic studies
The thermolysis of Ru3(CO)11[Ph2PC6H 5Cr(CO)3] affords two isomers of the benzyne derivative Ru3(CO)7(C6H4) [PPhC6H5Cr(CO)3]2 ((5) and (6)). The crystal structure of 5, previously determined, shows the phenyl groups are trans to the Ru3-triangle; in 6 they are probably cis and on the same side of the Ru3-triangle as the benzyne moiety. Os3(CO)11[Ph2PC6H 5Cr(CO)3] decomposes on heating to afford a benzyne derivative of a less common class Os3(CO)9(C6H4)[PC6H 5Cr(CO)3] (7), and an electron deficient molecule Os3(CO)8(PhPC6H4)[Ph 2PC6H5Cr(CO)3] (8), in which the PhPC6H4 moiety acts as a four-electron donor. The isopropylphosphine derivatives M3(CO)11[Pri2PC6H 5Cr(CO)3] (M=Ru, Os), also undergo thermolysis to afford HRu3(CO)8[C6H4Cr(CO) 3](PPri2) (10), Ru(CO)3[Pri2PC6H 5Cr(CO)3]2 (11), H2Os3(CO)8[PriPC6H 4Cr(CO)3] (12) and H2Os3(CO)8[PriPC6H 4Cr(CO)3] [Pri2PC6H5-Cr(CO)3] (13). Complex 10 is probably a benzynechromium tricarbonyl derivative with a Cr-Ru bond. The phosphines are trans in complex 11, a derivative of Ru(CO)5. The structures of complexes 12 and 13 are closely related and the orthometalated [PC6H4Cr(CO)3] moiety is acting as a four-electron donor to the cluster. Crystal data: for 8 (C41H24CrO11Os3P 2·CH2Cl2): monoclinic, a = 13.039(3), b = 18.001(2), c = 20.125(2) A?, β = 108.42(1)°, Z=4, space group P21/n; for 11 (C33H38Cr2O9P2Ru): monoclinic, a = 15.390(1), b = 10.241(2), c = 23.490(1) A?, β = 96.686(6)°, Z=4, space group P21/a; for 12 (C21H13CrO12Os3P): orthorhombic, a = 14.695(2), b = 16.696(2), c = 11.186(1) A?, Z = 4, space group P212121; for 13 (C35H32Cr2O14Os3P 2·2CH2Cl2): monoclinic, a = 11.536(2), b = 18.354(4), c = 23.176(3) A?, β = 98.43(2)°, Z = 4, space group P21/n. The structures were solved by Patterson methods and were refined by full-matrix least-squares procedures to R = 0.057, 0.031, 0.030 and 0.032 (Rw = 0.065, 0.030, 0.028 and 0.030) for 6320, 6103, 3529 and 6042 reflections with I ≥ 3σ (I), respectively.
Cullen, William R.,Rettig, Steven J.,Zhang, Hongli
p. 53 - 64
(2008/10/08)

Self-activation of a cluster-bound alkyne toward carbon-carbon bond forming reactions
The methanol-catalyzed elimination of Cl- from the activated anionic species [PPN][Ru3-(μ-Cl)(M-PhCCPh)(CO)9] (1) in the presence of bis(diphenylphosphino)methane (dppm) constitutes a rational high-yield route (>90%) to either the unique unsaturated 46-e (alkyne)-triruthenium cluster, Ru3(μ-PhCCPh)(CO)7(dppm) (2), or its 48-e CO adduct, Ru3(μ-PhCCPh)-(CO)8(dppm) (3). Whereas the CO-induced conversion of 2 into 3 is complete within few seconds at 25 °C under 1 atm of CO, the reverse transformation takes 1 h at 80 °C. The X-ray structure analysis of 2 is reported, revealing a perpendicular conformation of the alkyne relative to the metal triangle. The high reactivity of 2 is substantiated by a high chemical reactivity toward 2-e donors. Its reaction with 1 equiv of dppm (25 °C, 3 h) leads to the bis-dppm-substituted complex, Ru3(μ-PhCCPh)(CO)6(dppm)2 (4) (53% yield). Reaction of 2 with hydrogen gas (1 atm, 25 °C, 10 min) yields the dihydrido species, Ru3(μ-H)2(μ-PhCCPh)-(CO)7(dppm) (5) (89% yield) existing as a mixture of two isomers differing in the orientation of the alkyne relative to the edge-bridging dppm ligand. Complex 2 reacts with a terminal alkyne like phenylacetylene under mild conditions to afford a mixture of the fly-over type compound Ru3{μ-HCC(Ph)C(O)(Ph)CCPh}(dPPm)(CO)6 (6) (57% yield) and the diruthenacyclopentadiene derivative Ru2{μ-HCC(Ph)(Ph)CCPh}(μ-dppm)(CO)4 (7) (20% yield). The structure of 6 reveals the occurrence of a disymmetric edge-bridging dialkenyl ketone ligand HC=C(Ph)C(O)(Ph)C=CPh, resulting from regioselective coupling between the two alkynes and a carbonyl group. The formal unsaturation of 6 is masked by a weak interaction between the terminal C-Ph bond of the organic chain and one of the metal centers. Facile loss of this interaction is induced by mild thermolysis of 6. As a consequence, free rotation of the organic moiety around the metal-metal edge brings the opposite end of the organic chain (i.e., the C-H bond) close to the opposite face, thereby favoring CH activation to convert the alkenyl end into a vinylidene. This leads to quantitative formation of the vinylidene alkenyl ketone derivative, Ru3(μ-H){μ-CC(Ph)C(O)(Ph)CCPh}(dppm)(CO)6 (8) (94% yield). The X-ray structure of 8 is reported. Unsuccessful attempts to release the organic moiety from the cluster core are described. The reaction of a THF solution of 6 with CO in a reactor [P(CO) = 10 atm, T = 80 °C] leads to the new binuclear fly-over species Ru2{μ-HCC(Ph)C-(O)(Ph)CCPh}(CO)6 (9a), thereby indicating that elimination of the edge-bridging dppm and cluster fragmentation are more favorable than elimination of a free ketone from the intact cluster. The X-ray structure of Ru2{μ-HCC(C3H7)C(O)(Ph)CCPh}(CO)6 (9b) (resulting from the coupling between diphenylacetylene and 1-pentyne) is reported.
Rivomanana, Soa,Mongin, Carole,Lavigne, Guy
p. 1195 - 1207
(2008/10/08)