64364-79-0

Upstream product

• 15243-33-1 dodecacarbonyl-triangulo-triruthenium 
• 983-80-2 cis-1,2-bis-(diphenylphosphino)ethene 
• 15321-51-4 diiron nonacarbonyl 
• 88611-20-5 C₄₅H₅₀Cl₄P₂Ru₂ 
• 201230-82-2 carbon monoxide 
• 2071-20-7 bis-diphenylphosphinomethane 

Downstream Products

• 155706-55-1 1,1,1,2,2,2,3,3,3-nonacarbonyl-1,2-[μ-bis(diphenylphosphino)methane-P',P'']-3-(trimethyl phosphite-P)-triangulotriruthenium(0) 
• 465500-53-2 Ru₃(CO)9(C₆H₅)4P₂CH₂P(C₆H₁₁)3 
• 86768-37-8 Ru3(μ-dppm)(CO)9(PPh3) 
• 96502-43-1 Ru3(μ-PPhCH2PPh(C6H4))(CO)9 
• 155706-57-3 [Ru₃((C₆H₅)2PCH₂P(C₆H₅)2)(CO)9(P(C₆H₄CH₃)3)] 
• 96502-43-1 Ru₃(CO)9((C₆H₅)2PCH₂P(C₆H₅)C₆H₄) 
• 155706-56-2 [Ru₃((C₆H₅)2PCH₂P(C₆H₅)2)(CO)9(P(C₆H₄CH₃)3)] 

Relevant academic research and scientific papers

Synthesis and crystal structure of Ru3(μ3-NPh)(μ-DPPM)(CO)8

Reaction of Ru3(μ3-NPh)(CO)10 with DPPM (diphenylphosphinomethane) has given the substituted imido complex Ru3(μ3-NPh)(μ-DPPM)(CO)8, the structure of which has been determined by X-ray diffraction.The compound crystallizes in the monoclinic space group P21/n with a 14.027(7), b 14.887(7), c 18.499(9) Angstroem, β 93.52(4) deg and Z=4; R=0.022 and Rw=0.028 for 5006 independent reflections with I>3?(I).The interaction of the imido complex with CO has been investigated under various conditions.It proved to be very robust, giving small amounts of PhNCO (or PhNHCO2Me in the presence of methanol) and Ru3(μ-DPPM)(CO)10 only at 170 deg C and 60 atm of carbon monoxide.

Catalytic studies with ruthenium clusters substituted with diphosphines: Part I. Studies with Ru3(CO)10(Ph2PCH2PPh2)

The catalytic precursor Ru3(CO)10(Ph2PCH2PPh2)(dppm) (dppm = Ph2PCH2PPh2) isomerizes 1-hexene mainly to the kinetic product cis-2- hexene at low H2 pressure

Trapping of a phenyl group by a ruthenium cluster during dephenylation of coordinated CH2(PPh2)2 (dppm)

Pyrolysis of {Ru3( μ-dpp)(CO)9}n(dppa) (n = 1 or 2) afforded Ru3( μ3-PPhCH2PPh2)( μ3-η1:η2:P-C2PPh2)( μ-PPh2)(Ph)(CO)6, containing an Ru3 chain bridged by a dephenylated dppm ligand and by C2PPh2 and PPh2 ligands derived from the dppa ligand. The phenyl group from the dppm ligand has been trapped by one of the Ru atoms to give a rare example of a cluster-bound σ-Ph group. The molecular structure of Ru3(μ-H)(μ3-η1,η2-CCHP(O)Ph2}( μ-PPh2)( μdppm)(CO)6, obtained on one occasion from the mono-cluster complex, is also described.

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.

New ruthenium-tin clusters with bulky ligands. Crystal and molecular structures of [Ru2(CO)6(μ-SnR2)(μ-Ph 2PCH2PPh2)], [Ru3(CO)9(μ-SnR′2)3], [Ru3(CO)9(μ-SnR2)μ-SnR′ 2]2 and ...

Title full: New ruthenium-tin clusters with bulky ligands. Crystal and molecular structures of [Ru2(CO)6(μ-SnR2)(μ-Ph 2PCH2PPh2)], [Ru3(CO)9(μ-SnR′2)3], [Ru3(CO)9(μ-SnR2)μ-SnR′ 2]2 and [Ru3(CO)9(μ-SnR2) 2(μ-SnR′2)] [R = CH(SiMe3)2, R′= C6H2Pri3-2,4,6]. The first heterometallic clusters containing the SnR′2 (R′ = 2,4,6-triisopropylphenyl) moiety have been prepared. Triruthenium dodecacarbonyl reacted at low temperatures with SnR′2 or, at higher temperatures, with its trimer (SnR′2)3 to give both [Ru3(CO)10(μ-SnR′2)2] 1 and [Ru3(CO)9(μ-SnR′2)3] 2. Reaction of the pentametallic species [Ru3(CO)10(μ-SnL2)2] [L = R = CH(SiMe3]2 3 or R′] with SnR′2 or SnR2 respectively afforded the hexametallic clusters [Ru3(CO)9(μ-SnR2)(μ-SnR′ 2)2] 4 and [Ru3(CO)9(μ-SnR2) 2(μ-SnR′2)] 5. In the reaction of [Ru3(CO)12] with SnR2 the hexametallic cluster [Ru3(CO)9(μ-SnR2)3] 6 has now been isolated in addition to the previously reported Ru3Sn2 cluster. The trimer (SnR′2)3 also reacted with [Ru3(CO)10(dppm)] (dppm = Ph2PCH2PPh2) to give [Ru3(CO)8(μ-SnR′2)2(dppm)] 7, whereas with SnR2 the product was [Ru2(CO)6(μ-SnR2)(μ-dppm)] 8. Compound 7 can also be obtained by the reaction of 2 with dppm, using sodium-benzophenone to activate the cluster. Reaction of the dodecacarbonyl with Sn[CH(PPh2)2]2 or its lead analogue surprisingly did not yield a mixed cluster, but afforded a rapid and quantitative route to [Ru3(CO)10(dppm)]. Compound 2 behaves similarly, yielding 7 again in high yield. The crystal and molecular structures of 2,4, 5 and 8 have been determined. In compounds 2,4 and 5, the ruthenium triangle and the three tin atoms form a planar array. A detailed comparison of ligand steric effects is made. In 8 the metal atoms and the two P atoms are coplanar, with a long Ru-Ru vector bridged by the R2Sn group and the diphosphine [2.954(2) A]. The structure of 4 is unusual, the characteristic aryltin twist on only two of the three tin atoms generating chirality, resulting in a spiral packing in space group P65. This structure was determined both diffractometrically and using two different image-plate systems, and the results are remarkably consistent in all three cases.

CLUSTER CHEMISTRY. XXXXII. SOME RUTHENIUM CARBONYL COMPLEXES OF cis-1,2-BIS(DIPHENYLPHOSPHINO)ETHENE. X-RAY STRUCTURE OF Ru2(CO)6

A reaction between Ru3(CO)12 and cis-PPh2CH=CHPPh2 (ebdp), catalysed by , gave Ru3(μ-ebdp)(CO)10, which readily eliminated Ru(CO)4 on heating to form Ru2(μ-ebdp)(CO)6 in high yield.This complex has been fully characterised by an X-ray study, the ligand chelates one, nearly square-planar ruthenium, with the two phosphorus donors and bonds to the second, nearly trigonal bipyramidal ruthenium, via the C=C double bond.The Ru-Ru bond (2.8812(6) Angstroem) is formally a 2e donor bond from the square planar Ru to the trigonal bipyramidal Ru.The complex Ru2(CO)6 is monoclinic, space group P21/c with a 12.242(3), b 18.821(3), c 13.613(2) Angstroem, β 90.69(1) deg and Z = 4; 5036 independent data with I > 3?(I) were refined to R 0.034, R' 0.036.The reaction between Os3(CO)12 and ebdp gave only Os3(μ-ebdp)(CO)10.

Cluster Chemistry. Part 45. Synthesis and some Reactions of 3-PPhCH2PPh2)(CO)9>-: X-Ray Crystal Structures of (M = Cu, Ag, or Au)

Reactions between Ks3> and (E = P or As) afford solutions of the dephenylated anions, 3-EPhCH2EPh2)(CO)9>-, which can be reversibly protonated to give 3-EPhCH2EPh2)(CO)9>.The latter complexes may also been obtained directly from and H2 (20 atm, 80 deg C, 2 h) in cyclohexane (yields 65-75percent).Similar complexes were obtained in poor yield from .The group 1 B metal-containing clusters from 3-EPhCH2EPh2)(CO)9(PPh3)> (E = P, M = Cu, Ag, or Au; E = As, M = Au) were prepared from 3-EPh2CH2EPh2)(CO)9>- and sources of +; the analogues 3-PPh3CH2CH2PPh2)(CO)9(PPh3)> was also obtained.Single-crystal X-ray studies on the first three, title complexes showed that they are isostructural, the M(PPh3) fragment bridging the same Ru-Ru bond as that bridged by the PPh group of the face-capping phosphidophosphine ligand.Detailed examination of bond parameters in the Ru2MP moiety suggests that the three M(PPh3) fragments are not strictly isolobal, although it is the Ag(PPh3) fragment which interacts least strongly with the Ru3 core.The structures were refined by least-squares methods to residuals of 0.039, 0.044, and 0.041 for 4 560, 4 917, and 9 275 independent 'observed' reflections, respectively.

Kinetics of reaction of bis(diphenylphosphino)methane with dodecacarbonyltriruthenium

Reaction of dppm (Ph2PCH2PPh2) with Ru3(CO)12 proceeds via the complexes Ru3(CO)10(μ-dppm) and Ru3(CO)9(μ-dppm)(η1-dppm) to form the very stable Ru3(CO)8(μ-dppm)2, and the kinetics of the three reactions in benzene have been followed. Reaction with Ru3(CO)12 proceeds mainly by a ligand-dependent path, and dppm is about twice as nucleophilic as PPh3 toward this cluster. Ru3(CO)10(μ-dppm) reacts with dppm to form Ru3(CO)9(μ-dppm)(η1-dppm) by two paths. The main path (ca. 80%) follows kinetics characteristic of a reversible CO dissociative path. The minor path is completely inhibited by CO, even at high [dppm], and may involve dissociation of CO from an already substituted Ru atom before transfer of the unsaturation to the Ru(CO)4 moiety. The bridge formation reaction undergone by Ru3(CO)9(μ-dppm)(η1-dppm) to give the final product also occurs via two paths, but in this case they are of approximately equal importance. One is not affected by CO and is assigned to dissociative loss of CO from a bridged Ru atom, formation of the second bridge following very rapidly. The other may involve reversible loss of CO from the Ru(CO)3(η1-dppm) moiety followed by transfer of the unsaturation to one of the other Ru atoms.

Dehalogenation of binuclear arene-ruthenium complexes: A new route to homonuclear triruthenium and heteronuclear ruthenium-iron cluster complexes containing chelating phosphorus ligands. Crystal structure of Ru3(CO)10(Ph2PCH2PPh2)

The binuclear complexes (RuCl2(p-cymene))2(Ph2P(CH2) nPPh2) (2, n = 2; 4, n = 1) obtained from (RuCl2(p-cymene))2 have been reacted with an excess of Fe2(CO)9. The former derivative, 2, yielded FeRu(CO)8(Ph2PCH2CH2PPh2) (5), (Fe2Ru(μ-CO)2(CO)9)2(Ph 2PCH2CH2PPh2) (6), Ru3(μ-Cl)2(CO)8(Ph2PCH 2CH2PPh2) (7), and FeRu2(μ-Cl)2(CO)8(Ph2PCH 2CH2PPh2) (8) (noticeably, thermolysis of 8 under mild conditions yielded 7). The latter derivative, 4, afforded Ru3(CO)10(Ph2PCH2PPh2) (9) and FeRu2(CO)10(Ph2PCH2PPh2) (10). The X-ray crystal structure of 9 has been determined: monoclinic crystals, space group P21/c with a = 13.122 (3) A?, b = 12.040 (4) A?, c = 23.658 (7) A?, β = 103.44 (2)°, and Z = 4. Final R and Rw values are respectively 0.036 and 0.041 on the basis of 4346 independent reflections. The Ph2PCH2PPh2 group that bridges a Ru-Ru bond occupies equatorial positions. Interatomic distances of interest are Ru(1)-Ru(2) = 2.834 (1), Ru(1)-Ru(3) = 2.841 (1), and Ru(2)-Ru(3) = 2.860 (1) A?. The shortest bond Ru(1)-Ru(2) is supported by the chelating phosphorus ligand (Ru(1)-P(1) = 2.322 (2) and Ru(2)-P(2) = 2.334 (2) A?). Ru-P bonds are not coplanar as shown by the dihedral angle P(1)-Ru(1)-Ru(2)/P(2)-Ru(2)-Ru(1) = 19.1 (1)°. Such a distortion induces a disturbance in the distribution of CO ligands with respect to Ru3(CO)12. Of particular interest is the bending of every axial carbonyl toward one Ru-Ru bond.

CLUSTER CHEMISTRY. XXIX. PREPARATION OF CLUSTER COMPLEXES CONTAINING ARYLDIAZO LIGANDS: CRYSTAL STRUCTURE OF 3-PhAsCH2AsPh2)(CO)8>

Hydrogenation of (L2 = dppm or dpam) affords 3-PhECH2EPh2)(CO)9> (E = P or As), which is deprotonated by Ks3>.Reactions of the anions with give 3-PhECH2EPh2)(CO)9>, whi