Solid–Gas Hydrogenation of Hex-3-yne and 1,4-Cyclohexadiene in the Presence of the Clusters Ru3(CO)12, H4Ru4(CO)12, H2Ru4(CO)13, and H2FeRu3(CO)13 Supported on Inorganic Materials. Infrared Evidence for Surface Organometallic Reactions

The clusters Ru₃(CO)₁₂ (1), H₄Ru₄(CO)₁₂ (2), H₂Ru₄(CO)₁₃ (3), and H₂FeRu₃(CO)₁₃ (4) supported on pyrex borosilicate glass behave as catalysts for solid–gas hydrogenation reactions of hex-3-yne and 1,4-cyclohexadiene. Their activity and selectivity are discussed. Ru₃(CO)₁₂ (1) was also supported on inorganic oxides, normally used as chromatographic materials or supports for heterogeneous catalysis and characterized by different acidities and surface areas. The observed activities depend on the nature of the inorganic supports; the presence of water also has some influence. Some of these materials were characterized by HRTEM microscopy. Organometallic products have been collected after the catalytic runs both when pyrex and inorganic oxides were used as supports. In particular, the surface organometallic reactions of Ru₃(CO)₁₂ and H₄Ru₄(CO)₁₂ supported on silica have been followed by IR spectroscopy. The nature and role of the arising organometallic compounds are discussed. Our solid–gas results are in good agreement with the mechanisms previously proposed for the hydrogenation of comparable substrates under homogeneous conditions.     

Cluster synthesis. 42. The synthesis and crystal and molecular structures of the sulfur-bridged platinum-ruthenium carbonyl cluster compounds PtRu3(CO)9 L(PPh3)(μ3-S)2 (L=CO,PPh3) and PtRu4(CO)12(PPh3)(μ4-S)2

Two new mixed metal cluster complexes PtRu₃(CO)₁₀(PPh₃)(₃-S)₂,3 14% yield and PtRu₃(CO)₉(PPh₃)₂(₃-S)₂,4 23% yield were obtained from the reaction of Ru₃(CO)₉(₃-S)₂,1 with Pt(PPh₃)₂(C₂H₄) at 0°C. The cluster of4 consists of a spiked triangle of four metal atoms with two triply bridging sulfido ligands. The reaction of Ru₄(CO)₁₁(₄-S)₂,2 with Pt(PPh₃)₂(C₂H₄) yielded the expanded mixed-metal cluster complex PtRu₄(CO)₁₂(PPh₃)(₄-S)₂,5 in 12% yield. The structure of the cluster5 can be described as a pentagonal bipyramid of five metal atoms and two sulfido ligands with one metal-metal bond missing. Compounds4 and5 were characterized by a single-crystal X-ray diffraction analyses.     

Synthesis and structural characterization of mesitylphosphinidene-capped ruthenium and osmium clusters

Thermal reaction of [Ru₃(CO)₁₂] with PH₂Mes (Mes = mesityl) in refluxing toluene afforded mesitylphosphinidene-capped ruthenium carbonyl clusters, [Ru₃(CO)₉(μ-H)₂(μ₃-PMes)] (1), [Ru₃(CO)₈(PH₂Mes)(μ-H)₂(μ₃-PMes)] (2), [Ru₃(CO)₉(μ₃-PMes)₂] (3), [Ru₄(CO)₁₀(μ-CO)(μ₄-PMes)₂] (4), and [Ru₅(CO)₁₀H₂(μ₄-PMes)(μ₃-PMes)₂] (5). All products were fully characterized and structurally confirmed by X-ray crystal structure analysis. Complexes 2-4 were also obtained in high yields by stepwise reaction starting from 1. Fluxional behavior of carbonyl groups was observed in case of 4. Complex 5 reveals a new type of skeletal structure, bicapped-octahedron having μ₃- and μ₄-phosphinidene ligands at the capping positions. Similar reaction of [Os₃(CO)₁₂] with PH₂Mes yielded a phosphido-bridged osmium cluster [Os₃(CO)₁₀(μ-H)(μ-PHMes)] (6) and a phosphinidene-capped cluster [Os₃(CO)₉(μ-H)₂(μ₃-PMes)] (7).     

Glycal-ruthenium carbonyl clusters: Syntheses, characterization, and anticancer activity

Four new chiral ruthenium carbonyl cluster complexes Ru₃(μ-H)₂(CO)₉(L-2H) (1), Ru₃(μ-H)₂(CO)₇(L-2H)(dppm) (2), Ru₃(μ-H)₂(CO)₇(L-2H)(PPh₃)₂ (3), Ru₃(μ-H)₂(CO)₇(L-2H)(dppe) (4) containing a dehydrogenated form (L-2H) of 3,4,6-tri-O-benzyl-d-galactal (L) as a chiral ligand have been prepared and characterized. The anticancer activity of five compounds 1-4 and Ru₃(μ-H)₂(CO)₉(L-2H) 5 (L = tribenzyl glucal) against six types of human cancer cell lines was studied and compared to cisplatin. Compound 1 was chosen to produce more detailed growth curves based on overall highest activity profile. The structure of compound 2 was established by a single-crystal X-ray diffraction analysis. The structure based on triangular metal framework contains a bridging dehydrogenated tribenzyl galactal ligand bonded in a parallel μ₃-η²-bonding mode and a bridging dppm ligand. Variable-temperature NMR studies show that the two hydride ligands in compounds 1 and 2 are dynamically active on the NMR time scale at room temperature.     

Dppm-substituted ruthenium clusters with capping sulfido and selenido ligands derived from thiourea, tetramethylthiourea and elemental selenium

Treatment of [Ru₃(CO)₁₀(μ-dppm)] (4) [dppm = bis(diphenylphosphido)methane] with tetramethylthiourea at 66 °C gave the previously reported dihydrido triruthenium cluster [Ru₃(μ-H)₂(μ₃-S)(CO)₇(μ-dppm)] (5) and the new compounds [Ru₃(μ₃-S)₂(CO)₇(μ-dppm)] (6), [Ru₃(μ₃-S)(CO)₇(μ₃-CO)(μ-dppm)] (7) and [Ru₃(μ₃-S){η¹-C(NMe₂)₂}(CO)₆(μ₃-CO)(μ-dppm)] (8) in 6%, 10%, 32% and 9% yields, respectively. Treatment of 4 with thiourea at the same temperature gave 5 and 7 in 30% and 10% yields, respectively. Compound 7 reacts further with tetramethylthiourea at 66 °C to yield 6 (30%) and a new compound [Ru₃(μ₃-S)₂{η¹-C(NMe₂)₂}(CO)₆(μ-dppm)] (9) (8%). Thermolysis of 8 in refluxing THF yields 7 in 55% yield. The reaction of 4 with selenium at 66 °C yields the new compounds [Ru₃(μ₃-Se)(CO)₇(μ₃-CO)(μ-dppm)] (10) and [Ru₃(μ₃-Se)(μ₃-η³-PhPCH₂PPh(C₆H₄)}(CO)₆(μ-CO)] (11) and the known compounds [Ru₃(μ-H)₂(μ₃-Se)(CO)₇(μ-dppm)] (12) and [Ru₄(μ₃-Se)₄(CO)₁₀(μ-dppm)] (13) in 29%, 5%, 2% and 5% yields, respectively. Treatment of 10 with tetramethylthiourea at 66 °C gives the mixed sulfur-selenium compounds [Ru₃(μ₃-S)(μ₃-Se)(CO)₇(μ-dppm)] (14) and [Ru₃(μ₃-S)(μ₃-Se){η¹-C(NMe₂)₂}(CO)₆(μ-dppm)] (15) in 38% and 10% yields, respectively. The single-crystal XRD structures of 6, 7, 8, 10, 14 and 15 are reported.     

A study of the photochemistry and thermal chemistry of Ru3(CO)9(PR3)3{R = Ph,OMe} with two-electron donor ligands

The photochemistry of the tris-substituted clusters Ru₃(CO)₉(PR₃)₃ (R=Ph or OMe) with no added ligands, with CO, C₂H₄, alkynes and H₂ is compared and contrasted with results obtained for analogous thermal reactions. Photolysis of a CH₂Cl₂ solution of Ru₃(CO)₉(PPh₃)₃ leads to the metallated complex HRu₃(CO)₈(PPh₃)₂(PPh₂C₆H₄). In CCl₄, Ru(CO)₃(PR₃)Cl₂ is formed on photolysis of Ru₃(CO)₉(PR₃)₃. Photolysis of CO saturated solutions of Ru₃(CO)₉(PR₃)₃ leads to Ru(CO)₄(PR₃). C₂H₄ saturated solutions of Ru₃(CO)₉(PR₃)₃ generate the novel Ru(CO)₃(PR₃)(²-C₂H₄) complexes upon photolysis. With C₂H₂, photolysis of solutions of Ru₃(CO)₉(PR₃)₃ leads to the novel complexes Ru(CO)₃(PR₃)(²-C₂H₂). Substituted alkyne complexes have been prepared. Thermolysis of Ru₃(CO)₉(PR₃)₃ with HCCPh leads to the novel acetylide clusters HRu₃(CO)₆(PR₃)₃(₃-²-C₂Ph). With PhC CPh, only Ru₃(CO)₉{P(OMe)₃}₃ reacts, yielding the novel alkyne cluster Ru₃(CO)₆{P(OMe)₃}₃(₃-²-C₂Ph₂). With H₂, photolysis of CH₂Cl₂ solutions of Ru₃(CO)₉(PR₃)₃ leads to H₂Ru(CO)₂(PR₃)₂. Irradiating a 4:1 CH₂Cl₂ to EtOAc solution of Ru₃(CO)₉(PR₃)₃ under an atmosphere of H₂ leads to the novel dihydrido species H₂Ru₃(CO)₇(PR₃)₃. Thermolysis of H₂ saturated solutions of Ru₃(CO)₉(PR₃)₃ leads to H₄Ru₄(CO)₈(PR₃)₄.     

Ruthenium cluster compounds containing 1,1′-bis(diphenylphosphino)ferrocene (dppf): an electrochemical analysis and the crystal structure of [Ru3(CO)11]2(μ-dppf)

The electrochemistry of 1,1′-bis(diphenylphosphino)ferrocene (dppf) derivatives of Ru₃(CO)₁₂ was investigated. Two known compounds [Ru₃(CO)₈(μ-dppf)₂ (1) and Ru₃(CO)₁₀dppf (2)] and a new compound [Ru₃(CO)₁₁(μ-dppf)Ru₃(CO)₁₁ (3)] were prepared. Compound 3 was characterized spectroscopically and an X-ray crystal structure was obtained. The reductive electrochemistry of 1 and 2 showed an irreversible reduction and a follow-up oxidation, similar to Ru₃(CO)₁₂. The electrochemistry of compound 3 showed two irreversible waves and a follow-up oxidation. A trend in the reduction potential vs. the number of coordinated phosphorus atoms was noted. The oxidative electrochemistry of 1-3 showed a dppf-based chemically reversible wave, and an irreversible wave similar to that of Ru₃(CO)₁₂. Trends were also noted between the oxidation potential and the number of coordinated phosphorus atoms.     

Chalcogen-capped ruthenium carbonyl clusters derived from diphosphazane mono- and dichalcogenides of the type X2P(E)N(R)PX2 and X2P(E)N(R)P(E)X2 (E = S or Se)

Reactions of Ru₃(CO)₁₂ with diphosphazane monoselenides Ph₂PN(R)P(Se)Ph₂ [R = (S)-∗CHMePh (L⁴), R = CHMe₂ (L⁵)] yield mainly the selenium bicapped tetraruthenium clusters [Ru₄(μ₄-Se)₂(μ-CO)(CO)₈{μ-P,P-Ph₂PN(R)PPh₂}] (1, 3). The selenium monocapped triruthenium cluster [Ru₃(μ₃-Se)(μ_sb-CO)(CO)₇{κ²-P,P-Ph₂PN((S)-∗CHMePh)PPh₂}] (2) is obtained only in the case of L⁴. An analogous reaction of the diphosphazane monosulfide (PhO)₂PN(Me)P(S)(OPh)₂ (L⁶) that bears a strong π-acceptor phosphorus shows a different reactivity pattern to yield the triruthenium clusters, [Ru₃(μ₃-S)(μ₃-CO)(CO)₇{μ-P,P-(PhO)₂PN(Me)P(OPh)₂}] (9) (single sulfur transfer product) and [Ru₃(μ₃-S)₂(CO)₅{κ²-P,P-(PhO)₂PN(Me)P(OPh)₂}{μ-P,P-(PhO)₂PN(Me)P(OPh)₂}] (10) (double sulfur transfer product). The reactions of diphosphazane dichalcogenides with Ru₃(CO)₁₂ yield the chalcogen bicapped tetraruthenium clusters [Ru₄(μ₄-E)₂(μ-CO)(CO)₈{μ-P,P-Ph₂PN(R)PPh₂}] [R = (S)-∗CHMePh, E = S (6); R = CHMe₂, E = S (7); R = CHMe₂, E = Se (3)]. Such a tetraruthenium cluster [Ru₄(μ₄-S)₂(μ- CO)(CO)₈{μ-P,P-(PhO)₂PN(Me)P(OPh)₂}] (11) is also obtained in small quantities during crystallization of cluster 9. The dynamic behavior of cluster 10 in solution is probed by NMR studies. The structural data for clusters 7, 9, 10 and 11 are compared and discussed.     

Carbonyl substitution chemistry of some trimetallic transition metal cluster complexes with polyfunctional ligands

The trimetallic clusters [Ru₃(CO)₁₀(dppm)], [Ru₃(CO)₁₂] and [RuCo₂(CO)₁₁] react with a number of multifunctional secondary phosphine and tertiary arsine ligands to give products consequent on carbonyl substitution and, in the case of the secondary phosphines, PH activation. The reaction with the unresolved mixed P/S donor, 1-phenylphosphino-2-thio(ethane), HSCH₂CH₂PHPh ( LH₂), gave two products under various conditions which have been characterised by spectroscopic and crystallographic means. These two complexes [Ru₃(μ-dppm)(H)(CO)₇(LH)] and [Ru₃(μ-dppm)(H)(CO)₈(LH)Ru₃(μ-dppm)(CO)₉], show the versatility of the ligand, with it chelating in the former and bridging two Ru₃ units in the latter. The stereogenic centres in the molecules gave rise to complicated spectroscopic data which are consistent with the presence of diastereoisomers. In the case of [Ru₃(CO)₁₂] the reaction with LH₂ gave a poor yield of a tetranuclear butterfly cluster, [Ru₄(CO)₁₀(L)₂], in which two of the ligands bridge opposite hinge wingtip bonds of the cluster. A related ligand, HSCH₂CH₂AsMe(C₆H₄CH₂OMe), reacted with [RuCo₂(CO)₁₁] to give a low yield of the heterobimetallic Ru-Co adduct, [RuCo(CO)₆(SCH₂CH₂AsMe(C₆H₄CH₂OMe))], which appears to be the only one of its type so far structurally characterised.The secondary phosphine, HPMe(C₆H₄(CH₂OMe)) and its oxide HP(O)Me(C₆H₄(CH₂OMe)) also react with the cluster [Ru₃(CO)₁₀(dppm)] to give carbonyl substitution products, [Ru₃(CO)₅(dppm)(μ₂-PMe(C₆H₄CH₂OMe))₄], and [Ru₃H(CO)₇(dppm)(μ₂,η¹-P(O)Me(C₆H₄CH₂OMe))]. The former consists of an open Ru₃ triangle with four phosphide ligands bridging the metal-metal bonds; the latter has the O atom symmetrically bridging one Ru-Ru bond, the P atom being attached to a non-bridged Ru atom.     

The Thermolysis of [Ru3(CO)12] in Cyclohexene: Synthesis and Charaterisation of the New Clusters [Ru3H2(CO)9(μ3-η1:η2:η1-C6H8)] and [Ru5(CO)12(μ4-η2-C6H8)(η4-C6H8)]

Thermolysis of [Ru₃(CO)₁₂] in cyclohexene for 24 h affords the complexes [Ru(CO)₃(η⁴-C₆H₈)] (1), [Ru₃H₂(CO)₉(μ₂-η¹:η²:η¹-C₆H₈)] (2), [Ru₄(CO)₁₂(μ₄-C₆H₈)] (3) [Ru₄(CO)₉(μ₄-C₆H₈)(η⁶-C₆H₆)] (4a and 4b, two isomers) and [Ru₅(CO)₁₂(μ₄-η²-C₆H₈)(η⁴-C₆H₈)] (5), where 1, 3, 4a and 4b have been previously characterised as products of the thermolysis of [Ru₃(CO)₁₂] with cyclohexa-1,3-diene. The molecular structures of the new clusters 2 and 5 were determined by single-crystal X-ray crystallography, showing that two conformational polymorphs of 5 exist in the solid state, differing in the orientation of the cyclohexa-1,3-diene ligand on a ruthenium vertex.     

Synthesis of new heterometallic complexes by tin-sulfur bond cleavage of pySSnPh3 (pySH = pyridine-2-thiol) at triruthenium and triosmium centres

The ruthenium-tin complex, [Ru₂(CO)₄(SnPh₃)₂(μ-pyS)₂] (1), the main product of the oxidative-addition of pySSnPh₃ to Ru₃(CO)₁₂ in refluxing benzene, is [Ru(CO)₂(pyS)(SnPh₃)] synthon. It reacts with PPh₃ to give [Ru(CO)₂(SnPh₃)(PPh₃)(κ²-pyS)] (2) and further with Ru₃(CO)₁₂ or [Os₃(CO)₁₀(NCMe)₂] to afford the butterfly clusters [MRu₃(CO)₁₂(SnPh₃)(μ₃-pyS)] (3, M=Ru; 4, M=Os). Direct addition of pySSnPh₃ to [Os₃(CO)₁₀(NCMe)₂] at 70 °C gives [Os₃(CO)₉(SnPh₃)(μ₃-pyS)] (5) as the only bimetallic compound, while with unsaturated [Os₃(CO)₈{μ₃-PPh₂CH₂P(Ph)C₆H₄}(μ-H)] the previously reported [Os₃(CO)₈(μ-pyS)(μ-H)(μ-dppm)] (6) and the new bimetallic cluster [Os₃(CO)₇(SnPh₃){μ-Ph₂PCH₂P(Ph)C₆H₄}(μ-pyS)[(μ-H)] (7) are formed at 110 °C. Compounds 1, 2, 4, 5 and 7 have been characterized by X-ray diffraction studies.     

Ruthenium carbonyl clusters containing PMe2(nap) and derived ligands (nap = 1-naphthyl): generation of naphthalyne derivatives

Bis(dimethylphosphino)naphthalene, 1,8-(PMe₂)₂C₁₀H₆ (dmpn), reacts readily with Ru₃(CO)₁₂ or Ru₃(μ-dppm)(CO)₁₀ with replacement of one of the PMe₂ groups by H to give Ru₃(CO)_12 − n{PMe₂(nap)}_n (n = 1 2, 2 3) or Ru₃(μ-dppm)(CO)₉{PMe₂(nap)} 4; the complex Ru₃(CO)₁₀(dmpn) 1 is obtained only in small amount. Thermolysis of 2 or 4 gives Ru₃(μ-H)₂{μ₃-PMe₂(C₁₀H₅)}(μ-dppm)_n (CO)_8-2n (n = 0 5, 1 6, respectively) containing μ₃-naphthalyne groups.     

Easy Access to Phosphido-Selenido Clusters. Reaction of [Ru3(CO)12] with Ph2(pyth)PSe {pyth=5-(2-Pyridyl)-2-Thienyl} and Crystal Structure of [Ru3(μ3-Se)(μ-PPh2)(μ-pyth)(CO)6{P(pyth)Ph2}]

The reaction of [Ru₃(CO)₁₂] with Ph₂(pyth)PSe (pyth=5-(2-pyridyl)-2-thienyl) allows to obtain two novel clusters [Ru₃(₃-Se)₂(CO)₇{P(pyth)Ph₂}₂] 1 and [Ru₃(₃-Se)(-PPh₂)(-pyth)(CO)₆{P(pyth)Ph₂}] 2 in satisfactory yields. The first one exhibits the well-known bicapped, open triangular, 50-electron nido-core, whereas 2, whose crystal structure has been determined, shows the rather rare Ru₃Se tetrahedron with the Ph₂P and pyth fragments as side-bridging ligands. Morever cluster 2 belongs to the exiguous family of selenido-phosphido clusters not easily achievable by other routes.     

Electrochemical and Photochemical Conversion of [Ru3Ir(μ 3-H)(CO)13] into [Ru3Ir(μ-H)3(CO)12]

Electrochemical and photochemical properties of the tetrahedral cluster [Ru₃Ir( ₃-H)(CO)₁₃] were studied in order to prove whether the previously established thermal conversion of this cluster into the hydrogenated derivative [Ru₃Ir(-H)₃(CO)₁₂] also occurs by means of redox or photochemical activation. Two-electron reduction of [Ru₃Ir( ₃-H)(CO)₁₃] results in the loss of CO and concomitant formation of the dianion [Ru₃Ir( ₃-H)(CO)₁₂]^2–. The latter reduction product is stable in CH₂Cl₂ at low temperatures but becomes partly protonated above 283K into the anion [Ru₃Ir(-H)₂(CO)₁₂]^– by traces of water. The dianion [Ru₃Ir( ₃-H)(CO)₁₂]^2– is also the product of the electrochemical reduction of [Ru₃Ir(-H)₃(CO)₁₂] accompanied by the loss of H₂. Stepwise deprotonation of [Ru₃Ir(-H)₃(CO)₁₂] with Et₄NOH yields [Ru₃Ir(-H)₂(CO)₁₂]^– and [Ru₃Ir( ₃-H)(CO)₁₂]^2–. Reverse protonation of the anionic clusters can be achieved, e.g., with trifluoromethylsulfonic acid. Thus, the electrochemical conversion of [Ru₃Ir( ₃-H)(CO)₁₃] into [Ru₃Ir(-H)₃(CO)₁₂] is feasible, demanding separate two-electron reduction and protonation steps. Irradiation into the visible absorption band of [Ru₃Ir( ₃-H)(CO)₁₃] in hexane does not induce any significant photochemical conversion. Irradiation of this cluster in the presence of CO with _irr>340nm, however, triggers its efficient photofragmentation into reactive unsaturated ruthenium and iridium carbonyl fragments. These fragments are either stabilised by dissolved CO or undergo reclusterification to give homonuclear clusters. Most importantly, in H₂-saturated hexane, [Ru₃Ir( ₃-H)(CO)₁₃] converts selectively into the [Ru₃Ir(-H)₃(CO)₁₂] photoproduct. This conversion is particularly efficient at _irr >340nm.     

Products from the trimethylamine N-oxide activation reaction of Ru4(CO)12(μ 4-C6H8) with cyclohexa-1,3-diene

Summary Reaction of Ru₄(CO)₁₂( ₄-C₆H₈) (1) with three equivalents of Me₃NO and cyclohexa-1,3-diene in CH₂Cl₂ (195–295 K) gives one major product, the benzene butterfly cluster Ru₄(CO)₉( ₄-C₆H₈)( ⁶-C₆H₆) (2), in which the benzene is coordinated to a wing-tip Ru atom. Three other products are formed in lower yield, these comprised of an isomer of the aforementioned cluster in which the benzene is attached to a hinge Ru atom (3), the bis(cyclohexadiene) cluster Ru₄(CO)₈( ₄-C₆H₈)( ⁴-C₆H₈)₂ (4), and the trinuclear species Ru₃(CO)₈( ₃-C₆H₈)( ⁴-C₆H₈) (5). The characterization of the new compounds (4) and (5) is described, including the solid-state structure of (4) determined by a single crystal X-ray diffraction analysis.     

Ruthenium-tin complexes from the reaction of HSnPh3 with Ru3(CO)10(NCMe)2 and their reactions with bis(tri-t-butylphosphine)platinum

The compounds Ru₃(CO)₉(SnPh₃)₂(NCMe)(μ-H)₂ (1), Ru₃(CO)₁₀(SnPh₃)₂(μ-H)₂ (2), Ru(CO)₄(SnPh₃)₂ (3) and Ru(CO)₄(SnPh₃)(H) (4) were obtained from the reaction of Ru₃(CO)₁₀(NCMe)₂ with HSnPh₃ in hexane solvent. Compounds 1, 3 and the new compound Ru₃(CO)₇(SnPh₃)₃(NCMe)₂(μ-H)₃ (5) were obtained from reaction of Ru₃(CO)₁₀(NCMe)₂ with HSnPh₃ in a CH₂Cl₂ and MeCN solvent mixture. Compound 2 and the new compound Ru₃(CO)₉(SnPh₃)₃(μ-H)₃ (6) were obtained from reactions of 1 and 5 with CO, respectively. Compounds 2 and 6 eliminated benzene when heated to yield Ru₃(CO)₁₀(μ-SnPh₂)₂ (7) and Ru₃(CO)₉(μ-SnPh₂)₃ (8) which contain bridging SnPh₂ ligands. Compound 7 was found to react with to yield the adduct, (9) in 59% yield by the addition of groups to two of the Ru-Sn bonds to the bridging SnPh₂ ligands. Fenske-Hall molecular orbital calculations were performed to provide an understanding of the metal-metal bonding in the clusters of 7 and 9. Compounds 1, 2, 5, 6, 7 and 9 were characterized structurally by single crystal X-ray diffraction analysis.     

Reactions of 1,4-difeffocenylbuta-1,3-diyne and 1,4-diphenylbut-l-en-3-yne with Ru3(CO)12. Crystal structure of Ru3(CO)8(μ3-η-1-η1-η4-η2-C4Ph2(CH=CHPh)2)

Diyne FcCmCC.CFc (Fc is ferrocenyl) reacts with Ru₃(CO)₁₂ in boiling hexane to yield binuclear complexes Ru₂ and Ru₂(CO)₆(C₄Fc₂(C=CFc)₂C=O) containing ruthenacyclopentadiene and diruthenacycloheptadienone rings, respectively. The isomerism of the complexes is due to the different ways of coupling of the alkyne fragments of the diyne, namely, head-to-head, head-to-tail or tail-to-tail. The reaction of enyne PhC=CCH=CHPh with Ru₃(CO)₁₂ under similar conditions gives isomeric binuclear complexes Ru₂(CO)₆(C₄Ph₂(CH=CHPh)₂) and trinuclear clusters Ru₃(CO)₆(w-CO)₂(C₄Ph₂(CH=CHPh)₂) and Ru₃(CO)₈(₃-,¹-¹-⁴-² C₄Ph₂(CH=CHPh)₂). The structure of the latter was determined by X-ray diffraction analysis. The Ru₃ triangle coordinates eight terminal CO groups and the organic ligand resulting from the head-to-head dimerization of enyne molecules; the ruthenacyclopentadiene moiety is ⁴-coordinated to the Ru(CO)₂ group, and the third ruthenium atom is 2-bound to one of the PhCH=CH groups.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1261–1267, May, 1996.     

Reaction of the heteronuclear cluster RuOs3(μ-H)2(CO)13 with toluene

The heteronuclear cluster RuOs₃(μ-H)₂(CO)₁₃ (4) reacts with refluxing toluene to form the clusters Ru₂Os₃(μ-H)₂(CO)₁₆ (5) RuOs₃(CO)₉(μ-CO)₂(η⁶-C₆H₅Me) (6) and Ru₂Os₃(CO)₁₂(μ-CO)(η⁶-C₆H₅Me) (7). Cluster 5 exists as a mixture of five isomers. The inter-relationship among the clusters has also been investigated.     

Two gold-ruthenium clusters derived from Ru3(μ-H)3(μ3-CBr)(CO)9

The reaction between AuMe(PPh₃) and Ru₃(μ-H)₃(μ₃-CBr)(CO)₉ (1) affords the novel heptanuclear cluster Au₄Ru₃(μ₃-CMe)(Br)(CO)₉(PPh₃)₃ (2), containing an Au/Ru₃/Au trigonal pyramidal cluster face-capped by two Au(PPh₃) groups and a CMe ligand, together with Au₂Ru₃(μ-H)(μ₃-CMe)(CO)₉(PPh₃)₂ (3), formed by isolobal replacement of two of the three μ-H atoms in 1 by Au(PPh₃) groups. The latter co-crystallises with the analogous μ₃-CH complex, as also shown spectroscopically.     

Synthesis of homo- and heteronuclear ruthenium-gold clusters with diphosphine and thiolato bridged ligands. Single crystal molecular structure of [Ru3(CO)10(μ-AuPPh3)(μ-SC5H4N)] and [Ru3(CO)8(μ-H)(μ-SC5H4N)(μ-dppe)]

The reaction between [Ru₃(CO)₁₀(NCMe)₂] and [AuClPPh₃] gave compound [Ru₃(CO)₁₀(μ-Cl)(μ-AuPPh₃)] (1) in quantitative yield under very mild conditions. The reaction of 1 with 4-mercaptopyridine (4-pyS) using ultrasonic reaction conditions gave the heteronuclear compound [Ru₃(CO)₁₀(μ-AuPPh₃)(μ-SC₅H₄N)] (2) in moderate yield. There was no spectroscopic evidence that indicates the formation of the hydride isolobal analog in this reaction. The homonuclear cluster [Ru₃(CO)₈(μ-H)(μ-SC₅H₄N)(μ-dppe)] (3) was prepared by a selective reaction employing the ruthenium-diphosphine derivative [Ru₃(CO)₁₀(μ-dppe)] (dppe = 1,2-bis(diphenylphosphine)ethane) with 4-pyS in THF solution. The isolobal analog to compound 3, compound [Ru₃(CO)₈(μ-AuPPh₃)(μ-SC₅H₄N)(μ-dppe)] (4) was synthesized by the reaction between compound 2 and dppe in refluxing dichloromethane. Compounds 1-4 were characterized in solution by spectroscopic methods and the molecular structure of compounds 2 and 3 in the solid state was obtained by single crystal X-ray diffraction studies.