Cluster chemistry: XXXXVIII. Some reactions of Ru3(CO)12 with nitrogen heterocycles. X-ray crystal structures of Ru3(μ-CO)2(CO)8(bipy) and Ru3(μ-H){μ-N2C3H(CF3)2-3,5}(CO)10

Reactions between Ru₃(CO)₁₂ and the nitrogen heterocycles pyridine, 2,2′-bi-pyridyl, pyrazole, 3,5-dimethylpyrazole and 3,5-bis(trifluoromethyl)pyrazole are described. Pyridine afforded the cyclometallated complex Ru₃(μ-H)(μ-NC₅H₄)(CO)₁₀, which with excess pyridine formed Ru₃(μ-H)₂(μ-NC₅H₄)₂(CO)₈. 2,2′-Bipyridyl gave purple Ru₃(μ-CO)₂(CO)₈(bipy), shown by an X-ray structure to have an Fe₃(CO)₁₂-type structure, with the bipy chelating one of the CO-bridged Ru atoms. The pyrazoles gave Ru₃(μ-H)(μ-N₂CP₃HR₂)(CO)₁₀ (R = H, Me or CF₃), in which the pyrazolide ligand spans an RuRu bond also bridged by H, as shown by the X-ray structure of the CF₃ derivative. The bipyridyl and pyrazole complexes both crystallise in the monoclinic system, the former in space group P2₁/n with unit cell dimensions a 7.834(2), b 25.818(2), c 11.717(1) Å, β 107.41(1)° with Z = 4 and the latter in space group P2₁/c, unit cell dimensions a 16.802(3), b 7.726(1), c 18.807(3) Å, β 114.24(1)° with Z = 4. The structures were refined by conventional least-squares methods with the use of 3336 (2993 for the pyrazole structure) reflections with I > 2.5σ(I) to final R = 0.031 and R_w = 0.034 (0.025 and 0.026).     

Diphenylphosphine and diphenylphosphido derivatives of [Ru3(μ-H)(μ3-ampy)(CO)9] (Hampy = 2-amino-6-methylpyridine)

The reactions of [Ru₃(μ-H)(μ-ampy)(CO)₉] (1) (Hampy = 2-amino-6-methylpyridine) with one or two equivalents of PPh₂H lead to the complexes [Ru₃(μ-H)(μ₃-ampy)(CO)₈(PPh₂H)] (2) or [Ru₃(μ-H)(μ₃-ampy)(CO)₇(PPh₂H)₂] (3), in which the PPh₂H ligands are cis to the bridging NH fragment and cis to the hydride. Complex 2 can be transformed in refluxing THF into the phosphido-bridged derivative [Ru₃(μ₃-ampy)(μ-PPh₂)(μ-CO)₂(CO)₆] (4), which contains the PPh₂ ligand spanning one of the two RuRu edges unbridged by the amido moiety, and presents an extremely high ³¹P chemical shift of 386.9 ppm. Under similar conditions, complex 3 gives a mixture of two isomers of [Ru₃(μ-H)(μ₃-ampy)(μ-PPh₂)₂(CO)₆] in a 5:1 ratio; the major product (5) has a plane of symmetry, whereas the minor one (6) is asymmetric.     

Photoinduced formation of phosphido-bridged clusters derived from Ru3(CO)9(PPh2H)3. Crystal and molecular structure of Ru3(μ-H)(μ-PPh2)3(CO)7

The new complex Ru₃(CO)₉(PPh₂H)₃ (I) was prepared by the direct thermal reaction of Ru₃(CO)₁₂ with PPh₂ H and was spectroscopically characterized. Irradiation of I with λ ≥ 300 nm leads to the formation of Ru₂(μ-PPh₂)₂(CO)₆ (II) and three new phosphido-bridged complexes, Ru₃(μ-H)₂(μ-PPh₂)₂(CO)₈ (III), Ru₃(μ-H)₂(μ-PPh₂)₂(CO)₇(PPh₂H) (IV) and Ru₃(μ-H)(μ-PPh₂)₃(CO)₇ (V). These complexes have been characterized spectroscopically and Ru₃ (μ-H)(μ-PPh₂)₃(CO)₇ by a complete single crystal X-ray structure determination. It crystallizes in the space group P2₁/n with a 20.256(3), b 22.418(6), c 20.433(5) Å, β 112.64(2)°, V 8564(4) ų, and Z = 8. Diffraction data were collected on a Syntex P2₁ automated diffractometer using graphite-monochromatized Mo-K_α radiation, and the structure was refined to R_F 4.76% and R_wF 5.25% for the 8,847 independent reflections with F₀ > 6σ(F₀). The structure consists of a triangular array of Ru atoms with seven terminal carbonyl ligands, three bridging diphenylphosphido ligands which bridge each of the RuRu bonds, and the hydride ligand which bridges one RuRu bond. Complex IV was also shown to give V upon photolysis and is thus an intermediate in the photoinduced formation of V from I.     

Studies on the reactivity of the clusters [Ru3(CO)8(μ-H)2(μ-PR2)2] (R=But,Cy) towards phosphine ligands

The reaction behavior of the 48e-clusters [Ru₃(CO)₈(μ-H)₂(μ-PR₂)₂] (R=Bu^t, 1a; R=Cy, 1b) towards phosphine ligands has been studied. Whereas 1a reacts spontaneously with many phosphines at room temperature, a lack of reactivity for 1b under similar conditions is observed. Thus 1a reacts with dppm (Ph₂PCH₂PPh₂) to the known 46e-cluster [Ru₃(μ-CO)(CO)₄(μ₃-H)(μ-H)(μ-PBu^t₂)₂(μ-dppm)] (2a), and the reaction of 1a with dppe (Ph₂PC₂H₄PPh₂) yields analogously [Ru₃(μ-CO)(CO)₄(μ₃-H)(μ-H)(μ-PBu^t₂)₂(μ-dppe)] (3). Reactions of 1a with dmpm (Me₂PCH₂PMe₂), dmpe (Me₂PC₂H₄PMe₂) and PBuⁿ₃, respectively, gave in each case a mixture of products which could not be characterized. Contrary to the reaction behavior at room temperature, 1b reacts with phosphines in THF under reflux yielding the novel complexes [Ru₃(CO)₆(μ-H)₂(μ-PCy₂)₂L₂] (L=Cy₂PH, 4a; L=Bu^t₂PH, 4b; L=Ph₂PH, 4c; L=P(OEt)₃, 4d). 4a is also obtained directly by the reaction of [Ru₃(CO)₁₂] with an excess of Cy₂PH. The molecular structure of 4a has been determined by a single-crystal X-ray analysis. Moreover, the thermolysis of 1a in octane affords [Ru₃(CO)₈(μ-H)₂(μ₃-PBu^t)(Bu^t₂PH)] (6) as the main product, and the thermolysis of [Ru₃(CO)₉(Bu^t₂PH)(μ-dppm)] (7) yields 2a to a considerable extent. Treatment of 1a with carbon tetrachloride leads to [Ru₃(CO)₇(μ-H)(μ-PBu^t₂)₂(μ-Cl)] (8) as the main product.     

Synthesis of a μ4-PPh mixed metal cluster: the x-ray structures of [Ru3Rh2(CO)13(PEt3)(μ4-PPh)] and [Ru3Au(μ2-H)(CO)9(PMe2Ph)(μ3-PPh)]

The synthesis of a (μ₄-PPh) and some related (μ₃-PPh) mixed metal clusters containing ruthenium is described together with the X-ray structures of [Ru₃Rh₂(CO)₁₃(PEt₃)(μ₄-PPh)] and [Ru₃Au(μ₂-H)(CO)₉(PMe₂Ph)(μ₃-PPh)].     

Studies pertaining to the mechanism of “Pt(PCy3)“ addition. The reaction of MPt(μ-H)(μ-PnPr2)Pt(CO)(PCy3) with Pt(C2H4)2(PCy3)

The reaction of Pt(C₂H₄)₂(PCy₃) with (OC)₄M(μ-H)(μ-PⁿPr₂)Pt(CO)(PCy₃, (1: M  Cr, Mo, W) occurs in a highly specific, kinetically controlled manner to give MPt₂(μ²_MPt-CO)(η²_PtPt-H)(μ²_MPt-PⁿPr₂)(CO)₄ (PCy₃)₂ (5), as the first formed trimer. The trimer 5 (M  Mo, W) isomerizes to give MPt₂(μ²_PtPt-CO) ((μ²_MPtH)(μ²_MPt-PⁿPr₂)(CO)₄)PCy₃)₂ (6) which in turn isomerizes to MPt₂μ²_MPtCO)(μ²_MPt (μ²_PtPt-PⁿPr₂)(CO)₄(PCy₃)₂ (7, as the final isolable product. These results provide a detailed insight into the mechanism of “Pt(PCy₃) addition”, a cluster assembly process.     

Triosmium-antimony clusters containing the μ,η-phenylene ligand: Unusually long osmium-osmium bonds

The reaction of the osmium-antimony cluster Os₃(μ-H)(μ-SbPh₂)(μ₃,η²-C₆H₄)(CO)₉ with AsPh₃ at room temperature afforded the o-phenylene cluster Os₃(μ-H)(SbPh₂)(μ₂,η²-C₆H₄)(CO)₉(AsPh₃) by nucleophilic addition via a metal-metal bond cleavage, and the substitution product Os₃(μ-H)(SbPh₂)(μ₃,η²-C₆H₄)(CO)₈(AsPh₃). It reacted with ^tBuNC to afford the adduct Os₃(μ-H)(SbPh₂)(μ₂,η²-C₆H₄)(CO)₉(CN^tBu) quantitatively. This adduct isomerised slowly on standing via migration of the isonitrile, while photolysis led to decarbonylation to Os₃(μ-H)(SbPh₂)(μ₂,η²-C₆H₄)(CO)₈(CN^tBu). All the products have been characterised completely, including by X-ray crystallography, and their structures exhibit very long Os-Os bonds.     

Synthesis,characterization, and reactivity of a novel ruthenium carbonyl cluster containing tri-O-benzyl-d-glucal as a chiral carbohydrate ligand

A chiral carbohydrate ligand 3,4,6-tri-O-benzyl-d-glucal (L) reacts with the cluster triruthenium dodecacarbonyl Ru₃(CO)₁₂ giving a novel chiral cluster Ru₃(μ-H)₂(CO)₉(L-2H) (I) that shows fluxional behavior at room temperature. The reaction of Ru₃(μ-H)₂(CO)₉(L-2H) (I) with triphenylphosphine and diphenylphosphinoethane (dppe) gives two new clusters Ru₃(μ-H)₂(CO)₇(L-2H)(PPh₃)₂ (II) and Ru₃(μ-H)₂(CO)₇(L-2H)(dppe) (III). The new compounds I, II and III have been characterized by a combination of elemental analysis, mass spectrometry, infrared and variable temperature NMR spectroscopy.     

Open Pentaruthenium Cluster Complexes Formed from the Addition of Benzoic Acid to Ru<Subscript>5</Subscript>(C)(CO)<Subscript>15</Subscript>

Two isomers of Ru₅(C)(CO)₁₄(O₂CC₆H₅)(μ-H): Ru₅(C)(CO)₁₄(η²-O₂CC₆H₅)(μ-H), 2 and Ru₅(C)(CO)₁₄(μ-O₂CC₆H₅)(μ-H), 3 were obtained from the reaction of Ru₅(C)(CO)₁₅ with benzoic acid (PhCO₂H). Both compounds were characterized structurally by X-ray diffraction analysis. Compound 2 contains an opened pentaruthenium cluster with a chelating benzoate ligand on the ruthenium atom that was opened. Compound 3 contains an opened pentaruthenium cluster with a benzoate ligand on that bridges a pair of ruthenium atoms which are not mutually bonded. Compound 2 can be converted partially to 3 and 3 partially back to 2 and they form a 1.54/1.0 ratio (3/2) at equilibrium in solution at 95 °C.     

Cluster chemistry: XXXVIII. Reactions between M(C2R)(PR′3 (M = Cu,Ag, Au; R = Ph,C6F5; R′ = Me Ph) and H2Os3(CO)10: X-ray structures of Os3Au(μ-CHCHR)(CO)10(PPh3) (R = Ph and C6F5)

The reactions of Os₃(μ-H)₂(CO)₁₀ with a series of Group IB metal acetylide-tertiary phosphine complexes are described. Whereas the compounds M(C₂C₆F₅)(PPh₃) (M = Cu, Ag, Au) afforded the complexes MOs₃(μ-CHCHC₆F₅)(CO)₁₀(PPh₃) cleanly and in high yield, complex mixtures of products were obtained from reactions of the analogous phenylacetylides. The complexes MOs₃(μ-CHCHPh)(CO)₁₀(PPh₃), MOs₃(μ-CHCHPh)(CO)₉(PPh₃)₂ and MOs₃(μ-H)(CO)₁₀(PPh₃) (of known structure), and MOs₃(μ-CHCHPh)(CO)₉(PPh₃)₂ and HMOs₃(CHCPh)(CO)₈ (of unknown structure) were characterised; Au(C₂Ph)(PMe₃) afforded similar derivatives. The reactions proceed by oxidative-addition and hydrogen migration steps; MP bond cleavage reactions also occur to a small extent. The molecular structures of AuOs₃(μ-CHCHC₆R₅)(CO)₁₀(PPh₃) (R = F or H) were determined by X-ray analyses. For R = F, crystals are triclinic, space group P$\text{1}$ with a 9.081(2), b 13.291(2), c 17.419(2) Å, α 84.49(1), β 76.20(2), γ 75.81(2)° and Z = 2; 4622 observed data [I > 2.5σ(I)] were refined to R = 0.027, R_W = 0.031. For R = H, crystals are triclinic, space group P$\text{1}$, with a 9.403(4), b 13.448(3), c 13.774(4) Å, α 83.34(2), β 88.66(3), γ 70.21(3)°, and Z = 2; 4405 observed data [I > 2.5σ(I)] were refined to R = 0.030, R_W = 0.033. The two molecules differ in the orientation of the Ph rings of the PPh₃ groups, but are otherwise similar to Os₃(μ-H)(μ-CHCHBu^t)(CO)₁₀ with the μ-H ligand replaced by the isolobal μ-Au(PPh₃) group.     

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.     

Cluster chemistry: XXXIX. Gold—ruthenium clusters with sulphur ligands: Synthesis and structure of HRu3Au(μ3-S)(CO)9(PPh3), Ru3Au(μ3-SBut)(CO)9(PPh3) and Ru3Au2(μ3-S)(CO)9(PPh3)2

H₂Ru₃(μ₃-S)(CO)₉ is deprotonated by K[HBBu^s₃] to give cluster anions which react with [O{Au(PPh₃)}₃]⁺ or with AuCl(PPh₃)/T1⁺ to give HRu₃Au(μ₃-S)(CO)₉(PPh₃) (1) and Ru₃Au₂(μ₃-S)(CO)₉(PPh₃)₂ (3). A similar sequence with HRu₃(μ₃-SBu^t)(CO)₉ leads to Ru₃Au(μ₃-SBu^t)(CO)₉(PPh₃) (2) as the main product although some 1 also forms, indicating SC cleavage competes with deprotonation of HRu₃(μ₃-SBu^t)(CO)₉ by [HBBu^s₃]^?. The X-ray crystal structures of 1, 2 and 3 are described; (1) and (2) have “butterfly” AuRu₃ cores with markedly different hinge angles of 119 and 148° respectively, while 3 has a trigonal-bipyramidal Au₂Ru₃ skeleton. All three clusters have the sulphur atom symmetrically bridging the Ru₃ triangular face.     

Phosphor- und zinnhaltige metallacyclen des platins

The reaction of [Ru₃(CO)₁₂] with an equimolar amount of PPhH₂ under reflux leads not only to the formation of trinuclear products such as [Ru₃(μ₂-H)(μ₂-PPhH)(CO)₁₀] and [Ru₃(μ₂-H)₂(μ₃-PPh)(CO)₉] but to pentanuclear [Ru₄(μ₄-PPh)₂(μ₂-CO)(CO)₁₀] and to pentanuclear Ru₅(μ₄-PPh)(CO)₁₅]; the X-ray crystal structure of (Ru₄(μ₄-PPh)₂(μ₂-CO)(CO)₁₀] described.     

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.     

Synthesis and characterisation of hexanuclear ruthenium clusters containing a μ4-nitrene ligand. Crystal structures of [Ru6(CO)15(μ-CO)2(μ4NH)(μ-OMe)μ3-η2-N(H)C(O)OMe] and [Ru6(CO)16(μ-CO)2(μ4-NH)(μ-OMe)(μ-NCO)]

Two hexaruthenium carbonyl clusters [Ru₆(CO)₁₅(μ-CO)₂(μ₄-NH) (μ-OMe){μ₃-η²-N(H)C(O)OMe}] and [Ru₆(CO)₁₆(μ-CO)₂-(μ₄-NH)(μ-OMe)(μ-NCO)]2 have been isolated from the pyrolysis of H₂Ru₃(CO))₉NOCH₃, and single-crystal X-ray structure analysis shows that both 1 and 2 have a square planar arrangement of four ruthenium atoms capped by a μ₄-nitrene ligand, with two additional ruthenium atoms bridging two opposite RuRu edges of the square base to form a ‘boat’ form metal framework.     

Asymmetric acetylenic thioethers in ruthenium cluster chemistry

The compounds [Ru₃(CO)₉(μ,η²-SCCR)(μ₃,η²-CCR^′)] (R=SiMe₃, R^′=SiⁱPr₃ (1); R=SiⁱPr₃, R^′=SiMe₃ (2); R=SiⁱPr₃, R^′=H (3); R=H, R^′=SiⁱPr₃ (4)) have been obtained by cleavage of one S-C bond of the thioethers ⁱPr₃SiCCSCCR (R=H, SiMe₃) in the presence of Ru₃(CO)₁₂. Thermal treatment of [Ru₃(CO)₉(μ,η²-SCCSiⁱPr₃)(μ₃,η²-CCH)] yields to the cluster [Ru₄(CO)₉(μ-CO)₂(μ₄-S)(μ₄-η²-C(H)C)(CCSiⁱPr₃)] (5) which contains a bridging sulfur atom and a polycarbon chain as a consequence of the rupture of the S-C bond and a C-C coupling reaction. All derivatives have been characterized by spectroscopic data. An X-ray diffraction study was carried out on the species [Ru₃(CO)₉(μ,η²-SCCSiⁱPr₃)(μ₃,η²-CCSiMe₃)] and of [Ru₃(CO)₉(μ,η²-SCCSiⁱPr₃)(μ₃,η²-CCH)].     

Novel heterobimetallic complexes with S2CPR3(κ-S,S′)(κ-S,C,S′) bridges. X-Ray structure of [MnMo(CO)6(μ-Br)-(μ-S2CPiPr3)]

Reaction of fac-[Mn(CO)₃(S₂CPR₃)(Br)] with [Mo(CO)₃(NCMe)₃] produces a member of a novel class of heterodinuclear complex [MnMo(CO)₆(μ-Br)(μ-S₂CPR₃)] (R = Cy, ⁱPr), which contains S₂CPR₃ bridging ligands, acting as an (κ-S,S′) chelate towards Mn, and as an (κ-S,C,S′) pseudoallyl group to Mo, without a direct MoMn bond. One carbonyl group in [MnMo(CO)₆(μ-Br)(μ-S₂CPR₃)] can be easily displaced at room temperature by neutral ligands such as PEt₃ and P(OMe)₃, affording pentacarbonyl complexes, [MnMo(CO)₅(L)(μ-Br)(μ-S₂CPR₃].     

Conversion of a phenylphosphinidene-capped ruthenium cluster compound with a closo-octahedral Ru4P2 framework to one with a closo-trigonal prismatic skeleton by the addition of carbon monoxide and protons

Treatment of [Ru₄(μ₄-PPh)₂(μ₂-CO)(CO)₁₀] with NaBH₄ leads to the formation of [Ru₄(μ₄-PPh)₂(μ₂-H)(μ₂-CO)₂(CO)₈]⁻ which readily adds protons and carbon monoxide to produce [Ru₄(μ₃-PPh)₂(μ₂-H)₂(CO)₁₂]; X-ray crystallographic studies have revealed that while the Ru₄P₂ framework adopts a closo octahedral geometry in [Ru₄(μ₄-PPh)₂(μ₂-H)(μ₂-CO)₂(CO)₈]⁻, it adopts a closo trigonal prismatic one in [Ru₄(μ₃-PPh)₂(μ₂-H)₂(CO)₁₂]     

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.