Vincent Ferrand

Amphiphilic organoruthenium oxomolybdenum and oxovanadium clusters

Abstract Para-cymene ruthenium dichloride dimer reacts in aqueous solution with sodium molybdate or sodium vanadate to give the amphiphilic clusters [ (η6-p-MeC6H4i Pr) 4Ru4Mo4O16] (1) and [ (η6-p-MeC6H4i Pr) 4 Ru4V6O19] (4) respectively. The analogous reaction of hexamethylbenzene ruthenium dichloride dimer with sodium vanadate gives [ (η6-C6Me6) 4Ru4V6O19] (5) . The mixed-metal clusters [ (η6-p-MeC6H4i Pr) Ru (η5-C5Me5) 3Rh3Mo4O16] (2) and [ (η6-p-MeC6H4i Pr) 2Ru2 (η5-C5Me5) 2Rh2Mo4O16] (3) are accessible from a mixture of para-cymene ruthenium dichloride dimer and pentamethylcyclopentadienyl rhodium dichloride dimer with sodium molybdate in aqueous solution. The crystal structure analyses of 1 and 4 reveal different framework geometries of the metal oxygen skeletons. 17O NMR spectroscopy and partial charge calculations confirm the presence of three different types of oxygen atoms in 1.

The mixed-metal carbonyl cluster anion [Os3Ir(CO)13]- : synthesis, structure, reactivity and catalytic activity in the carbonylation of methanol

The cluster anion [Os3Ir(CO)13]− (1) was prepared in 50% yield by reaction of Os3(CO)12 with [Ir(CO)4]−. The single-crystal X-ray structure analysis of the bis(triphenylphosphoranylidene)ammonium salt shows 1 to consist of a tetrahedral metal core with one of the 13 carbonyl ligands being bridging. Protonation of 1 led to the neutral cluster HOs3Ir(CO)13 (2), whereas the hydrogenation gave the cluster anion [H2Os3Ir(CO)12]− (3). The catalytic activity of 1 for the carbonylation of methanol was studied. Using CH3I as co-catalyst, catalytic turnover numbers up to 1800 were obtained (140°C, 30 bar) within 14 h.

Carboncarbon coupling reactions on triruthenium clusters: synthesis and structure of Ru3(CO)9[μ3-η3-PhCCCC(H)Ph][μ2-NS(O)MePh] and Ru3(μ2-CO)(CO)7[μ3-η3-PhCCCC(H)Ph][μ3-NS(O)MePh]

The reaction of the electron-deficient cluster ( μ 2 -H)Ru 3 (CO) 9 [ μ 3 -NS(O)MePh] ( 1 ) with para -nitrotolane gives, with coupling of two alkyne units and elimination of the para -nitrophenyl fragment, the trinuclear complexes Ru 3 (CO) 9 [ μ 3 - η 3 -PhCCCC(H)Ph][ μ 2 -NS(O)MePh] ( 2 ) and Ru 3 ( μ 2 -CO)(CO) 7 [ μ 3 - η 3 -PhCCCC(H)Ph][ μ 3 -NS(O)MePh] ( 3 ). The resulting organic moiety, coordinated as μ 3 - η 3 -5e-donor best considered as a butenynyl (PhCCCC(H)Ph) ligand in 2 and as a butatrienyl (PhCCCC(H)Ph) ligand in 3 . From the reaction mixture, the two isomeric vinyl complexes Ru 3 ( μ 2 -CO) 2 (CO) 6 [ μ 2 - η 2 -PhCC(H)(C 6 H 4 - p -NO 2 )][ μ 3 - NS(O)MePh] ( 4a ) and Ru 3 ( μ 2 -CO) 2 (CO) 6 [ μ 2 - η 2 -(C 6 H 4 - p -NO 2 )C C(H)Ph]-[ μ 3 -NS(O)MePh] ( 4b ) complexes can also be isolated.

Triruthenium clusters containing vinyl ligands: synthesis and structure of Ru3(μ2-CO)2(CO)6[μ3-NS(O)MePh](μ2-η1,η2-PhCH2CCH2), Ru3(μ2-CO)(CO)7[μ3-NS(O)MePh](μ3-η1,η2-PrnCCHPrn, Ru3(μ2-CO)(CO)7[μ3-NS(O)MePh](μ3-η1,η2-PhCCHBun), and (μ2-H)Ru3(CO)6(μ2-η1,η2-PhCCHPh)(μ3-μ1,η2-PhCCPh)[μ3-η1,η2-NS(O)Me(C6H4)]

Abstract The electron-deficient cluster (μ2-H(Ru3(CO)9[μ3-NS(O)MePh] (1) reacts with the terminal alkyne PhCH2CCH to give the vinyl complex Ru3(μ2-CO)2(CO)6[μ3-NS(O)MePh](μ2-η1,η2-PhCH2CCH2)(2). The analogous reaction with internal alkynes (RCCR′) affords the clusters Ru3(μ2-CO)(CO)7[μ3-NS(O)MePh](μ3-η1,η2-RCCHR′) (3 R = R′ = Prn; 4: R = Ph: R′= Bun) in which the vinyl ligand has opened a RuRu bond upon coordination the Ru3 framework. In the case of diphenylacetylene, reaction with two equivalents of the alkyne, yields the vinyl-alkyne cluster (μ2-H)Ru3(CO)6(μ2-η1,η2-PhC  CHPh)(μ3-η1,η2-PhCCPh)[μ3-η1,η2-NS(O)Me(C6H4)] (5) with ortho-metallation of the phenyl substituent of the sulfoximido cap.

[(p-PriC6H4Me)4Ru4Mo4O16]: an amphiphilicorganoruthenium oxomolybdenum cluster presenting a unique frameworkgeometry

The amphiphilic title compound, easily accessible from (p- cymene)ruthenium dichloride dimer and sodium molybdate in aqueous solution, presents an unprecedented Ru 4 Mo 4 O 12 framework comprising a central Mo 4 O 4 cube with four folded ORuO flaps resembling the sails of a windmill.

Electron-deficient triruthenium and triosmium clusters from the reaction of the cluster anions [HM3(CO)11]− (M=Ru, Os) with tricyclohexylphosphine in methanol

Abstract The reaction of Na[HRu 3 (CO) 11 ] with an excess of tricyclohexylphosphine in methanol gives the neutral complex H 2 Ru 3 (CO) 6 (PCy 3 ) 3 which is the first 44 e − triruthenium cluster reported. This highly electron-deficient species reacts with carbon monoxide to give the saturated 48 e − cluster Ru 3 (CO) 9 (PCy 3 ) 3 . The electronic structure of the novel 44 e − cluster was established by EHT and DFT molecular orbital calculations of isoelectronic model compounds. The analogous reaction of [N(PPh 3 ) 2 ][HOs 3 (CO) 11 ] with PCy 3 in methanol affords the 46 e − cluster H 2 Os 3 (CO) 7 (PCy 3 ) 3 , the first trisubstituted derivative of H 2 Os 3 (CO) 10 . In all cases methanol acts as source of protons for the formation of the hydrido clusters.

Carbon–carbon coupling reactions of but-2-yne on a triruthenium framework: synthesis and molecular structure of Ru3(CO)7[NS(O)MePh](HCMeCMeCMeCMeCO) and Ru3(CO)8(CMeCMeCMeCMe)

Abstract The cluster HRu3(CO)9[NS(O)MePh] (1) reacts with two equivalents of MeCCMe in tetrahydrofuran at 60°C to give the dienonyl derivative Ru3(CO)7[NS(O)MePh](HCMeCMeCMeCMeCO) (2), along with an isomer mixture of Ru3(CO)8[NS(O)MePh](HCMeCMe) (3). At 100°C, the same reaction gives rise to the formation of the diendiyl cluster Ru3(CO)8(CMeCMeCMeCMe) (4). The single-crystal structure analyses reveal for 2 a closed Ru3 skeleton and for 4 an open Ru3 framework.

Electron counting and bonding analysis in triruthenium clusters containing sulfoximido ligands: true or false electron-deficient systems?

Triruthenium clusters containing a methylphenylsulfoximido cap or bridge, Ru3(CO)9(μ2-H)[μ3-NS(O)MePh] (1), Ru3(CO)10(μ2-H)[μ3-NS(O)MePh] (2), Ru3(CO)8(μ3-η2-CPhCHBu)[μ3-NS(O)MePh] (3), Ru3(CO)9(μ3-η2-PhCCCCHPh)[μ2-NS(O)MePh] (4), and Ru3(CO)7(μ2-CO)(μ3-η2-PhCCCCHPh)[μ3-NS(O)MePh] (5) have been examined by EHT and DFT calculations in order to analyze the bonding present in the clusters and to establish the electron counting. They clearly show that a μ3-sulfoximido group is not a 3e− ligand as one may be led to think at first sight, but rather acts as a three-orbital/5e− system, i.e. should be considered as isolobal to an NR− ligand. Because of some delocalization of its π-type orbitals on the sulfur and oxygen atoms, it is expected to bind slightly less strongly to metal atoms than classical imido ligands. Once in a μ2 coordination mode, the sulfoximido ligand retains a lone pair on its pyramidalized N atom and becomes a two-orbital/3e− ligand. It follows that clusters 1, 2, 4 and 5 are electron-precise, whereas cluster 3 is electron deficient with respect to the 18e− rule but obeys the polyhedral skeletal electron pair electron-counting rules. Consistently, all the calculated clusters exhibit large HOMO–LUMO gaps and no trace of electron deficiency can be found in their electronic structures.

Saturated and unsaturated triruthenium clusters containing three sterically demanding phosphine ligands: synthesis and structure of [Ru3(CO)9(PCy3)3] and [Ru3H2(CO)6(PCy3)3]

The reaction of Na[Ru3H(CO)11] with an excess of tricyclohexylphosphine in methanol afforded, depending on the reaction conditions, the tri-substituted clusters [Ru3(CO)9(PCy3)3] (48e) and [Ru3H2(CO)6(PCy3)3] (44e), inaccessible hitherto.

The mixed-metal carbonyl cluster anion [Ru3Ir(CO)13]–: synthesis, molecular structure, fluxionality, reactivity†

The new cluster anion [Ru3Ir(CO)13]–1 was synthesized in high yield from [Ru3(CO)12] and [Ir(CO)4–. The single-crystal X-ray structure analysis of the bis(triphenylphosphoranylidene)ammonium salt revealed the presence of two isomers, [Ru3Ir(CO)11(µ-CO)2]–1a and Ru3Ir(CO)9(µ-CO)4]–1b in the same crystal. Both 1a and 1b present a tetrahedral Ru3Ir framework, differing only by the number of bridging carbonyl ligands. Variable-temperature 13C NMR spectroscopic studies of 1 revealed the fluxionality of the carbonyl ligands and the interconversion of both isomers in solution. Protonation of 1 gave the neutral cluster [HRu3Ir(CO)13] 2, whereas reaction of 1 with molecular hydrogen yielded the anion [H2Ru3Ir(CO)12]–3. Either hydrogenation of 2 or protonation of 3 gave [H3Ru3Ir(CO)12] 4. The tetrahedral structure of the hydrido derivatives was confirmed by a single-crystal X-ray structure analysis of the bis(triphenylphosphoranylidene)ammonium salt of 3.