34438-91-0

Upstream product

• 5112-95-8 bis(diphenylphosphino)acetylene 
• 15243-33-1 dodecacarbonyl-triangulo-triruthenium 
• 100-47-0 benzonitrile 
• 205441-17-4 Ru₃(CO)11(PPh₃) 
• 892-20-6 triphenylstannane 
• 2816-43-5 triphenylgermane 
• 97633-58-4 HRu₃(CH₃OCCHCC₆H₅)(CO)9 
• 84349-76-8 Ru₃(CO)10(P(C₆H₅)2(C₆H₄CHCH₂)) 
• 116198-00-6 {Ru3(CO)10(PPh3)2} 
• 82532-28-3 (Ru₃(CO)11)2(1,2-bis(diphenylphosphino)ethane) 
• 86276-91-7 Ru₃(CO)11(P(C₆H₅)(OCH₃)2) 
• 4071-99-2 1-hydrido-1-methyl-2,3,4,5-tetraphenyl-1-silacyclopentadiene 
• 39774-25-9 6-phenylpyridin-2-amine 
• 29890-10-6 tetracarbonylbis(acetonitrile)tungsten 

Downstream Products

• 73037-72-6 (μ-H)4Ru4(CO)10(PPh2Me)2 

Relevant academic research and scientific papers

Heterometallic Boride Clusters: Formation of Octahedral (-)(M = Rh or Ir) and Gold(I) Phosphine Derivatives. Crystal Structures of , trans-> and cis->

The reaction of the butterfly cluster (-) with led to the octahedral boride (-) 1.In solution, 11B NMR spectroscopic evidence supports the presence of both cis- and trans-isomers of 1.The trans form is predominant.When treated with >, 1 yielded > 3 in two isomeric forms 3a and 3b.Similar reactions occur with other phosphine gold(I) derivatives.The crystal structure of compound 3a has been determined and reveals a trans arrangement of Rh atoms and a face capping AuP(C6H11)3 unit.The anion (-) reacted with (L = cyclooctene or L2 = cycloocta-1,5-diene) under a stream of CO to give (-) 2; the crystal structure of 2 has been determined and confirms an octahedral metal framework with trans iridium atoms.Cluster 2 reacted with > to yield > 4 and crystallographic data for 4 show that the Ir atoms are mutually cis in the octahedral Ir2Ru4 skeleton.The AuP(C6H11)3 unit bridges the Ir-Ir edge.In (-), the four ruthenium atoms define a butterfly framework with the boron atom lying in a semi-interstitial position.The addition of two Group 9 metal atoms to close up the metal cage to an octahedral one with an M2Ru4 core should initially give a cis isomer.In fact the trans isomer is observed for both 1 and 2, although for 1 both cis and trans isomers are observed by 11B NMR spectroscopy.Geometrical preferences which accompany the addition of a gold(I) phosphine fragment to anions 1 and 2 to give 3 and 4 respectively are discussed.

Preparation and characterization of the square-based pyramidal cluster anion 4-COH)>

The new compound 4-COH)>, , (PPN = bis(triphenylphosphine) iminium) is a product in several cluster expansion reactions which use triruthenaboranes as precursors, although the yields are not high.An X-ray diffraction study has shown that in the anion 1 has a square-based pyramidal framework of ruthenium atoms.With the square face capped by a μ4-COH group.Studies of the reactivity of 1 have been carried out, but have not shown 1 to be a ready precursor to an Ru5C-carbido species as had been expected.Keywords: Ruthenium; Carbonyl; Cluster; Crystal structure

Synthesis and Crystal Structure of (μ-H)Ru3(CO)10(μ-NH-CH2Ph). An Example of Activation of the Carbon-Nitrogen Triple Bond

The neutral complex (μ-H)Ru3(CO)10(μ-NH-CH2Ph) was obtained by reductive co-ordination of benzonitrile to Ru3(CO)12 in the presence of acetic acid and its structure was elucidated by an X-ray analysis.

Tetraruthenium carbonyl complexes containing germyl and stannyl ligands from the reactions of Ru4(CO)13(μ-H)2 with HGePh3 and HSnPh3

The compounds Ru4(CO)12(GePh3) 2(μ-H)4, 1 and Ru4(CO) 12(SnPh3)2(μ-H)4, 2 were obtained from the reactions of Ru4(CO)13(μ-H)2 with HGePh3 and HSnPh3, respectively. Both compounds contain a nearly planar butterfly structure for the four metal atoms with two GePh 3/SnPh3 ligands and four bridging hydride ligands around the periphery of the cluster. When heated, 1 and 2 were converted into the complexes Ru4(CO)12(μ4-EPh)2, 3, E = Ge, and 4, E = Sn, by cleavage of two phenyl groups from each of the GePh3 ligands. Compounds 3 and 4 contain square planar arrangements of the four ruthenium atoms with quadruply bridging germylyne and stannylyne ligands on opposite sides of the square plane. The bonding and electronic transitions of 3 were analyzed by DFT computational analyses.

Triruthenium, hexaruthenium, and triosmium carbonyl derivatives of 2-amino-6-phenylpyridine

The triruthenium cluster complexes [Ru3(μ-H) (μ3-η2-HapyPh-N,N)(CO)9 ] (1) and [Ru3(μ-H)2(μ3-η3- HapyC6H4-N,N,C)2(CO)6] (2) and the hexaruthenium ones [Ru6(μ3-H)2 (μ5-η2-apyPh-N,N)(μ-CO)2 (CO)14] (3) and [Ru6(μ3-H) (μ5-η3-apyC 6H4-N,N,C) (μ-CO)3 (CO)13] (4) have been prepared from [Ru3(CO)12] and 2-amino-6-phenylpyridine (H2apyPh). Compound 1 contains a deprotonated HapyPh ligand capping a face of the metal triangle. Compound 2 contains two cyclometalated HapyC6H4 ligands, each spanning a Ru-Ru edge through the N atom of the amido fragment and chelating the remaining Ru atom through both the pyridine N atom and the C atom of the cyclometalated ring. The hexanuclear derivatives 3 and 4 have an uncommon basal edge-bridged square pyramidal metallic skeleton. The bridging ligand of 3 is a doubly deprotonated apyPh ligand which caps the metallic square through the exocyclic N atom, while is attached to the Ru atom that bridges the edge of the square pyramid through the pyridine N atom. Complex 4 is structurally related to 3 but has a cyclometalated phenyl ring. It has been established that compound 2 is formed by reaction of 1 with H2apyPh and that complex 3 is formed by reaction of 1 with [Ru3(CO)12]. While the hydrogenation of 4 gives 3, the thermolysis of 3 gives 4 among other unidentified products. The reaction of the osmium cluster [Os3(CO)10 (MeCN)2] with H2apyPh gives a 1:5 mixture of the edge-bridged decacarbonyl derivatives [Os3(μ-H)(μ- η1-HapyPh-N)(CO)10] (5) and [Os3(μ-H) (μ-η2-HapyPh-N,N)(CO)10] (6). Both compounds give the face-capped nonacarbonyl derivative [Os3(μ-H)- (μ3-η2-HapyPh-N,N) (CO)9] (7) upon irradiation with UV light. Curiously, while complexes 5 and 7 are stable in refluxing toluene, the thermolysis of 6 gives a mixture of 5, 7, and the cyclometalated dihydride [Os3(μ-H)2(μ- η3-HapyC6H4-N,N,C)(CO)9] (8).

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 =

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

Mono- and Di-dentate Tertiary Phosphine and Monodentate Tertiary Phosphite Derivatives of

The reactions of the butterfly cluster with a range of tertiary phosphines and diphosphines and with a large excess of trimethyl phosphite have been explored.Twenty-two derivatives of the general types 12-x(PR3)xBH2> (x=1 or 2), 12-xxBH2> (x=2-4), Ru4H(CO)11(L-L)BH2>, and 2> (L-L=diphosphine) have been synthesised and characterised by mass spectrometry and IR and multinuclear NMR spectroscopies.The single-crystal structures of , trans-2BH2> and *CH2Cl2 (dppe=Ph2PCH2CH2PPh2) have been determined.In the PPh3 ligand occupies a wing-tip equatorial site.In 2BH2> the two P(OMe)3 ligands are also in such sites and both the isomers in which these ligands are mutually cis or trans with respect to the cluster core are formed; the solid-state structure of the trans isomer has been confirmed.When the two phosphorus-donor atoms are provided in the form of a didentate ligand the sites of co-ordination depend upon the nature of the backbone of the ligand.In , the dppe ligand bridges a Rwing tip-Ruhinge edge and two isomers are observed in solution; the solid-state structure of one isomer has been elucidated.Use of the diphosphine ligands allows the formation of linked dicluster species, and the competition for the formation of linked and monocluster species in which the ligand behaves in either a mono- or di-dentate fashion has been investigated.In the case of dppa an additional product when the ligand is in a four-fold excess is in which both dppa ligands are pendant and co-ordinated to different wing-tip ruthenium atoms.

CLUSTER CHEMISTRY LI. REACTIONS OF SOME SUBSTITUTED RUTHENIUM AND OSMIUM CLUSTER CARBONYLS WITH DIHYDROGEN. X-RAY CRYSTAL STRUCTURES OF Ru3(μ-H)2(μ3-PPh)(CO)8(PMePh2),Ru4(μ-H)4(μ-dppm)(CO)10, Ru4(μ-H)3(μ3-PPhCH2PPh2)(CO)10 AND Os3(μ-H)2(μ-dppm)(CO)8

The reaction of dihydrogen (80 deg C, 20bar, 2h) with a series of tertiary phosphine and phosphite complexes Ru3(CO)12-n(L)n (L=PMe3, PPh3' PPh (OMe)2 or P(OMe)3; n= 1-3), and with complexes containing dppm, dppe, dpam and PPh2(C6H4CH=CH2-2) have been studied.Complexes containing monodentate ligands gave tetranuclear complexes Ru4(μH)4(CO)12-n(L)n (n= 0-3, but not 4). whereas complexes with bidentate ligamnds showed varying behaviour.Thus Ru3(μ-dppm)(CO)10 gaveRu3(μ-H)2(μ3-PPhCH2PPh2)(CO)9, further hydrogenation of which afforded Ru3(μ-H)2(μ3-PPh)(CO)8(PMePh2).Ru3(μ-dppe)(CO)10 gave a mixture of Ru3(μ-H)(μ3-PPhCH2CH2PPh2)(CO)9 and Ru4(μ-H)4(μ-dppe)(CO)10 at the major products, and Ru3(μ-η 2,P-CH2=CHC6H4PPh2)(CO)10 gave a mixture of Ru4(μ-H)4(CO)12-nn (n=0 and 1).Pyrolysis of Ru4(μ-H)4(μ-dppm)(CO)10 afforded Ru4(μ--H)3(μ3-PPhCH2PPh2)(μ-CO)2(CO)8.The molecular structures of Ru3(μ-H)2(μ3-PPh))(CO)8(PMePh2), Ru4(μ-H)4(μ-dppm)(CO)10 and Ru4(μ-H)3(μ-PPhCH2PPh2)(μ-CO)2(CO)8 have been determined: 2286, 4930 and 6393 data (I=>2,5ρ(I)) were refined to R and Rw values of 0.032 and 0.037, 0.026 and 0.035 and 0.043 and 0.053, respectively.Hydrogenation of Os3(μ-dppm)(CO)10 gave Os3(μ-H)2(μ-dppm(CO)8, whose structure was also determined: 3367datawith I>=2.5ρ(I) were refined to R 0.044, Rw 0.052.

Methylidyne-alkyne coupling on triruthenium clusters and hydrogenation of cluster-bound 1,3-dimetalloallyl units. A new model for Fischer-Tropsch chain growth

Alkylidyne-alkyne coupling occurs upon reaction of H3Ru3(μ3-CX)(CO)9 (X = OMe, Me, Ph, or CH2CH2CMe3) at 25 °C or HRu3(μ-CX)(CO)10 (X = OMe) at 60 °C with alkynes R1C2R2, forming 1,3-dimetalloallyl clusters HRu3(μ3-η3-XCCRCR)(CO)9 (X = OMe, (R1, R2) = (H, H), (Me, Me), (Ph, Ph), (H, Ph), (H, CMe3), (H, n-Bu), (H, CO2Me), (Ph, CO2Me), (H, OEt); X = Ph, (R1, R2) = (Ph, Ph); X = Me, (R1, R2) = (Me, Me); X = CH2CH2CMe3, (R1, R2) = (Ph, Ph)) in yields of 15-90%. In an analogous fashion, HOs3(μ-COMe)(CO)10 and PhC2Ph yield HOs3(μ3-η3-MeOCCPhCPh)(CO)9. One equivalent of the appropriate cis-alkene is formed from reduction of alkyne by H3Ru3(μ3-CX)(CO)9. With unsymmetrical alkynes the relative amounts of the two possible regioisomers depend upon the alkyne substituents. Coupling from either H3R3(μ3-COMe)(CO)9 or HRu3(μ-COMe)(CO)10 forms HRu3(μ3-η3-MeOCCR1CR 2)(CO)9 in the relative amounts (R1, R2) = (H, Ph)/(Ph, H), 3:1, (H, n-Bu)/(n-Bu, H), 2:1, (H, CMe3,)/(CMe3, H), 20:1, (H, CO2Me)/(CO2Me, H), 2:1, (H, OEt)/(OEt, H), 1:0, (Me, C7-H15, Me), 3:1, and (CO2Me, Ph)/(Ph, CO2Me), 2:1. Hydrogenation (90 °C, 1-4 atm) of HRu3(μ3-η3MeOCCR1CR 2)(CO)9 ((R1, R2) = (H, H), (H, CMe3), (Me, Me), (Ph, Ph), (H, OEt), (H, Ph), (H, n-Bu), (n-Bu, H), (H, CO2Me)) produces in each case the corresponding H3Ru3(μ3CCHR1CH2R 2)(CO)9 in yields of 6-43%; also formed are substantial quantities of H4Ru4(CO)12. Hydrogenation of DRu3(μ3-η3-MeOCCHCCMe 3)(CO)9 produces exclusively H3Ru3(μ3-CCH2CHDCMe 3)(CO)9. This alkylidyne-alkyne coupling and subsequent hydrogenation to form an alkylidyne of longer carbon chain length suggests a mechanism to account for 2-methylated hydrocarbon products in the Fischer-Tropsch reaction.