The synthesis of heteronuclear clusters containing cyclopentadienyl- or pentamethylcyclopentadienyliridium and ruthenium or osmium

The reaction of Cp*Ir(CO)₂ or CpIr(CO)₂ with Ru₃(CO)₁₂ under a hydrogen atmosphere afforded the heterometallic clusters Cp*IrRu₃(μ-H)₂(CO)₁₀ and CpIrRu₃(μ-H)₂(CO)₁₀, respectively, in moderate yields. In the former reaction, the tetrahydrido cluster Cp*IrRu₃(μ-H)₄(CO)₉ was also formed in trace amounts, although this cluster can be obtained in high yields by the hydrogenation of Cp*IrRu₃(μ-H)₂(CO)₁₀; the Cp analogue was not obtainable. The reaction of Os₃(μ-H)₂(CO)₁₀ with Cp*Ir(CO)₂ afforded the osmium analogue Cp*IrOs₃(μ-H)₂(CO)₁₀ in 70% yield, along with a trace amount of the pentanuclear cluster Cp*IrOs₄(μ-H)₂(CO)₁₃. Hydrogenation of Cp*IrOs₃(μ-H)₂(CO)₁₀ afforded Cp*IrOs₃(μ-H)₄(CO)₉ in excellent yield. The reaction of Cp*Ir(CO)₂ with Os₃(CO)₁₀(CH₃CN)₂ afforded the known trinuclear cluster Cp*IrOs₂(CO)₉ and the novel cluster Cp*IrOs₃(CO)₁₁. Solution-state NMR studies show that the hydrides in the iridium-ruthenium clusters are highly fluxional even at low temperatures while those in the iridium-osmium clusters are less so.     

Activation of the carbon—nitrogen triple bond of benzonitrile in the presence of triosmium clusters and acetic acid. Crystal structure of (μ-H)Os3(CO)10(μ-O2CCH3), a product of the reaction

The activation of the CN triple bond of benzonitrile in the presence of acetic acid and of Os₃(CO)₁₂ or H₂Os₃(CO)₁₀ has been studied. When Os₃(CO)₁₂ reacts with PhCN and acetic acid in refluxing n-octane the three main products are (μ-H)Os₃(CO)₁₀(μ-O₂CCH₃) (I), (μ-H)Os₃(CO)₁₀(μ-NCHPh) (II) and (μ-H)Os₃(CO)₁₀(μ-NHCH₂Ph) (III); II and III are analogues of (μ-H)Ru₃(CO)₁₀(μ-NCHPh) and (μ-H)Ru₃(CO)₁₀(μ-NHCH₂Ph) obtained from PhCN, Ru₃(CO)₁₂ or H₄Ru₄(CO)]₁₂, and acetic acid. In contrast to the reaction with ruthenium clusters, Os₃(CO)₁₂ and H₂Os₃(CO)₁₀ also give the adduct Os₃(CO)₁₀(CH₃COOH) (I). The structure of I has been fully elucidated by X-ray diffraction. Crystals of I are monoclinic, space group P2₁/m, with unit cell parameters a 7.858(6), b 12.542(8), c 9.867(6) Å, β 109.92(2)°, Z = 2. In I an edge of the triangular cluster of osmium atoms is doubly bridged by a hydride and an acetate ligand. Ten terminal carbonyl groups are bonded to the metal atoms.     

Reactions of metal carbonyl cluster complexes with multidentate phosphine ligands; reactions with bis(diphenylphosphino)methane

Reactions of Rh₆(CO)₁₆ with bis(diphenylphosphino)methane (dppm) gave Rh₆(CO)₁₄(dppm), Rh₆(CO)₁₂(dppm)₂, or Rh₆(CO)₁₀(dppm)₃, depending upon the reaction conditions. Rh₄(CO)₁₀(dppm) may be obtained from the reaction of Rh₄(CO)₁₂ with dppm, but this derivative rapidly decomposes in solution to give Rh₄(CO)₈(dppm)₂, Rh₆(CO)₁₄(dppm), and Rh₆(CO)₁₂(dppm)₂. Ir₄(CO)₁₀(dppm) and Ir₄(CO)₈(dppm)₂ have also been prepared, and their structures are discussed on the basis of infrared and ³¹P NMR spectroscopic data.     

Syntheses of double- and triple-decker clusters of osmium and cobalt metals linked by cyclotetradeca-1,8-diyne ligands

Photoirradiation of Os₃(CO)₁₀(C₁₄H₂₀) (1) in n-hexane produces the double-decker cluster [Os₃(CO)₉(C₂₈H₄₀)] [Os₃(CO)₁₀] (7), which can also be prepared from the reaction of Os₃(CO)₉(C₂₈H₄₀) (2) and Os₃(CO)₁₀(NCMe)₂. Further reaction of 7 with Os₃(CO)₁₀(NCMe)₂ affords the triple-decker cluster [Os₃(CO)₉(C₂₈H₄₀)][Os₃(CO)₁₀]₂ (8). The bis(diyne) complex Os₃(CO)₈(C₁₄H₂₀)₂ (3) reacts with Os₃(CO)₁₀(NCMe)₂ sequentially to yield the double-decker cluster [Os₃(CO)₈(C₁₄H₂₀)₂][Os₃(CO)₁₀] (4) and the triple-decker cluster [Os₃(CO)₈(C₁₄H₂₀)₂][Os₃(CO)₁₀]₂ (5). Treatment of 3 with Co₂(CO)₈ at room temperature leads to the mixed-metal triple-decker cluster [Os₃(CO)₈(C₁₄H₂₀)₂][Co₂(CO)₆]₂ (6), while the reaction of 2 and Co₂(CO)₈ produces [Os₃(CO)₉(C₂₈H₄₀)][Co₂(CO)₆]₂ (9) and [Os₂(CO)₆(C₂₈H₄₀)][Co₂(CO)₆]₂ (10). Compound 10, which involves cluster degradation from Os₃ to Os₂, has been structurally characterized by an X-ray diffraction study.     

Triosmium clusters containing diphosphine and triphosphine ligands

The isomeric butadiene compounds 1,1- and 1,2-[Os₃(C₄H₆)(CO)₁₀] and the acetonitrile compound 1,2-[Os₃(CO)₁₀(MeCN)₂] react with the diphosphines Ph₂P(CH₂)_nPPh₂ (n = 2, 3 or 4) to give separable isomers of [Os₃(CO)₁₀(diphosphine)] in which the diphosphine is either bridging or chelating, whereas dppm (n = 1) gives only the 1,2-isomer. The mono-acetonitrile compound [Os₃-(CO)₁₁(MeCN)] reacts to give two series of compounds: [Os₃(CO)₁₁(diphosphine)], containing one coordinated and one free phosphorus atom, and [Os₆(CO)₂₂(diphosphine)] with two Os₃(CO)₁₁ groups bridged by the diphosphine. The triphosphine, Ph₂PCH₂CH₂PPhCH₂CH₂PPh₂ (triphos), reacts similarly to give two separable isomers of [Os₃(CO)₁₁(triphos)] and two inseparable isomers of [Os₆(CO)₂₂(triphos)]. Whereas [Os₃(CO)₁₁(dppm)] readily undergoes decarbonylation to give 1,2-[Os₃(CO)₁₀(dppm)], other compounds of the type [Os₃(CO)₁₁(diphosphine)] are not decarbonylated under the same conditions, but react with Me₃NO to give the 1,2-but not the 1,1-isomers of [Os₃(CO)₁₀(diphosphine)].     

Addition reactions of a polynuclear osmium hydrido compound leading to associative carbonyl substitution and catalytic alkene isomerisation

The ability of H₂Os₃(CO)₁₀ to undergo addition reactions under mild conditions allows associative CO substitution via isolable intermediates of the type H₂Os₃(CO)₁₀ (L = CO, PMe₂Ph, PPh₃ or PhCN) whose spectra and structures are discussed. It is probable that simple addition of alkenes to H₂Os₃(CO)₁₀ is in part responsible for its facile catalysis of alkene isomerisation. The kinetics of catalytic conversion of terminal to internal alkenes and of allylic alcohols to aldehydes or ketones are reported and discussed. The reactions of H₂Os₃(CO)₁₀ with allylic halides to give the complexes HOs₃X(CO)₁₀ and Os₃X₂(CO)₁₀ where X = Cl, Br or I are described. Compound H₂Os₃(CO)₁₀ complies with the 18ρ-rule but nevertheless has a chemistry much like that of coordinatively unsaturated molecules.     

Reaction of ethylene with the unsaturated cluster complex H2Os3 (CO)10

Treatment of H₂Os₃(CO)₁₀ with excess ethylene forms ethane and a hydridovinyl cluster complex HOs₃(CO)₁₀(CHCH₂), which rearranges in refluxing octane to the vinylidene complex H₂Os₃(CO)₉(CCH₂).     

Triosmium carbonyl clusters of sulfur and oxygen mixed donor ligands

The reaction of the lightly stablized cluster [Os₃(CO)₁₀(NCMe)₂] with thiosalicylic acid affords two products [{Os₃(CO)₁₀(µ-H}]₂SC₆H₄CO₂],1 and [Os₃H(CO)10SC₆,H₄C(O)OOs₃H(CO)₁₁],2. Complex 2 undergoes CO dissociation to give1 or fragmentation to give [Os₃H(CO)10SC₆H₄ COOH], 3 in solution. Reaction of phthalic acid and [ Os₃(CO)₁₀(NCMc)₂] gives two products [{Os₃(CO)₁₀(µ-H)}₂O₂CC₆H₄CO₂], 4 and [Os₃H(CO)₁₀O₂CC₆ H₄C(O)OOs₃H(CO)₁₁], 5. 5 also undergoes CO dissociation to give4, but no such conversion is observed in the preparation of [{Os₃(CO)₁₀(µH)}₂ (SC₆H₄S)],6 from the reaction betweeno-dithiobenzene and [Os₃(CO)₁₀ (NCMe)₂]. Unlike thiosalicylic acid, treatment of [Os₃(CO)₁₀(NCMe)₂] with 1 equivalent 2,2'-dithiosalicylaldehyde in dichloromethane produces the compounds [Os₃(CO)₁₀(SC₆H₄CHO)₂],7 and [Os₃(CO)₁₀µ-H)(SC₆H₄CHO)].8 in moderate yields which are stable in both the solid state and solution. The mechanism for the formation of1-5 is also proposed. All the clusters1-8 have been fully characterized by conventional spectroscopic methods and the structures of1, 3, 4, 7, and8 have been established by X-ray, crystallography.     

Cage Opening of a Carborane Ligand by Metal Cluster Complexes

The reaction of Os₃(CO)₁₀(NCMe)₂ with closo‐o‐C₂B₁₀H₁₀ has yielded two interconvertible isomers Os₃(CO)₉(μ₃‐4,5,9‐C₂B₁₀H₈)(μ‐H)₂ ( 1 a ) and Os₃(CO)₉(μ₃‐3,4,8‐C₂B₁₀H₈)(μ‐H)₂ ( 1 b ) formed by the loss of the two NCMe ligands and one CO ligand from the Os₃ cluster. Two BH bonds of the o‐C₂B₁₀H₁₀ were activated in its addition to the osmium cluster. A second triosmium cluster was added to the 1 a / 1 b mixture to yield the complex Os₃(CO)₉(μ‐H)₂(μ₃‐4,5,9‐μ₃‐7,11,12‐C₂B₁₀H₇)Os₃(CO)₉(μ‐H)₃ ( 2 ) that contains two triosmium triangles attached to the same carborane cage. When heated, 2 was transformed to the complex Os₃(CO)₉(μ‐H)(μ₃‐3,4,8‐μ₃‐7,11,12‐C₂B₁₀H₈)Os₃(CO)₉(μ‐H) ( 3 ) by a novel opening of the carborane cage with loss of H₂.     

The effect of pressure on electronic excitations in Mn2(CO)10 and Re2(CO)10

The shift with pressure has been measured for the σ → σ* excitations for crystalline Mn₂(CO)₁₀ and Re₂(CO)₁₀ to 120 kbar. The results are interpreted in terms of the relative importance of the effect of compression on stabilization of the bonding vis-a-vis the antibonding orbitals, and the importance of the van der Waals interaction with the surroundings. The π → σ* excitation in Mn₂(CO)₁₀ and the σ → π* excitation in Re₂(CO)₁₀ are briefly discussed.     

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.     

Zinn(IV)-Mangancarbonyl-Cluster mit offener und geschlossener Metall–Metall-Verknüpfung aus Umsetzungen von SnX2 (X = Halogen) mit Mn2(CO)10

The Formation of Tin(IV)-Manganesecarbonyl Clusters with Open and Closed Metal?Metal Skeleton by Reaction of SnX₂ (X = Halogen) with Mn₂(CO)₁₀ The oxidative addition of SnX₂ (X = Br, I) and Mn₂(CO)₁₀ results in the product X₂Sn[Mn(CO)₅]₂, the clusters of this type are final reaction products in a bomb tube. The starting materials SnX₂ (X = Cl, Br, I) and Mn₂(CO)₁₀ lead in a manifold CO overpressure discharged Schlenk tube mainly to the formation of th new clusters of the type Mn₂(CO)₈[μ-Sn(X)Mn(CO)₅]₂ (X = Cl, Br, I). It was possible to prepare Mn₂(CO)₈[μ-Sn(Br)Mn(CO)₅]₂ by an application of the Schlenk tube technique with the reaction systems: Br_4?nSn[Mn(CO)₅]_n (n = 1, 2)/Mn₂(CO)₁₀ (or BrMn(CO)₅)/Xylol and BrSn[Mn(CO)₅]₃/Xylol. FSn[Mn(CO)₅]₃ could be prepared with SnF₂ and Mn₂(CO)₁₀ in a bomb tube.     

Synthesis and characterisation of linked triosmium clusters using the bis(diphenylphosphino)acetylene ligand

The reaction of Os₃(CO)₁₁(NCMe) with bis(diphenylphosphino)acetylene (dppa) at room temperature affords [Os₃(CO)₁₁]₂(dppa) (1) in good yield, while Os₃(CO)₁₀(NCMe)₂ with an excess of dppa gives [Os₃(CO)₁₀(dppa)]₃ (2) and [Os₃(CO)₁₀(dppa)]₄ (3) in moderate yields. The structure of 1 has been determined by a single crystal X-ray diffraction study.     

Reactions of triosmium clusters with organic azides; x-ray crystal structures of [Os3(CO)10(NCMe)(N3COPh)], [Os3(μ-H)(CO)10(HN3Ph)], and [Os3(μ-H)2(CO)9(μ3-NPh)]

Organic azides [N₃R] react with [Os₃(CO)₁₁(NCMe)] and with [Os₃(μ-H)₂(CO)₁₀] to form [Os₃(CO)₁₀(NCMe)(N₃COR)] (R  Ph) and [Os₃(μ-H)(CO)₁₀(HN₃R)] (R  Ph, n-Bu, CH₂Ph, cyclo-C₆H₁₁), respectively; the latter may be converted to [Os₃(μ-H)₂(CO)₉(μ₃-NR)] by thermolysis; the molecular structure of the phenyl derivative of each class of compound has been confirmed by x-ray analysis.     

Negative ion mass spectra of Os3(CO)12X2 and Os3(CO)10X2 complexes (X = Br,I)

The negative-ion mass spectra at 70 eV of the compounds Os₃(CO)₁₂X₂ and Os₃(CO)₁₀X₂ (X =Br, I) are reported. Negative molecular ions are absent and only Os₃-containing fragments due to the loss of carbonyl groups are observed. [M  CO]^? is the base peak in the spectrum of Os₃(CO)₁₀I₂ and has a very high abundance in that of Os₃(CO)₁₀Br₂, whereas it is very weak in the spectra of Os₃(CO)₁₂X₂, where [M  3 CO]^? is the base peak. This change in the ionic intensities is related to the closed and open structure of the Os₃ unit in Os₃(CO)₁₀X₂ and Os₃(CO)₁₂X₂ respectively.     

Neue Phosphor-verbrückte Übergangsmetallcarbonyl-Komplexe Die Kristallstrukturen von [Re2(CO)7(PtBu)3], [Co4(CO)10(PtBu)2], [Ir4(CO)6(PtBu)6] und [Ni4(CO)10(PiPr)6]

New Phosphorus-bridged Transition Metal Carbonyl Complexes. The Crystal Structures of [Re₂(CO)₇(P^tBu)₃], [Co₄(CO)₁₀(P^tBu)₂], [Ir₄(CO)₆(P^tBu)₆], and [Ni₄(CO)₁₀(PⁱPr)₆], (P^tBu)₃ reacts with [Mn₂(CO)₁₀], [Re₂(CO)₁₀], [Co₂(CO)₈] and [Ir₄(CO)₁₂] to form the multinuclear complexes [M₂(CO)₇(P^tBu)₃] (M = Re ( 1 ), Mn ( 5 )), [Co₄(CO)₁₀(P^tBu)₂] ( 2 ) and [Ir₄(CO)₆(P^tBu)₆] ( 3 ). The reaction of (PⁱPr)₃ with [Ni(CO)₄] leads to the tetranuclear cluster [Ni₄(CO)₁₀(PⁱPr)₆] ( 4 ). The complex structures were obtained by X-ray single crystal structure analysis: ( 1 : space group P1 (Nr. 2), Z = 2, a = 917.8(3) pm, b = 926.4(3) pm, c = 1 705.6(7) pm, α = 79.75(3)°, β = 85.21(3)°, γ = 66.33(2)°; 2 : space group C2/c (Nr. 15), Z = 4, a = 1 347.7(6) pm, b = 1 032.0(3) pm, c = 1 935.6(8) pm, β = 105.67(2)°; 3 : space group P1 (Nr. 2), Z = 4, a = 1 096.7(4)pm, b = 1 889.8(10)pm, c = 2 485.1(12) pm, α = 75.79(3)°, β = 84.29(3)°, γ = 74.96(3)°; 4 : space group P2₁/c (Nr. 14), Z = 4, a = 2 002.8(5) pm, b = 1 137.2(8) pm, c = 1 872.5(5) pm, β = 95.52(2)°).     

Synthesis and characterisation of HRuRh3(CO)12. Crystal structures of HRuRh3(CO)12, HRuRh3(CO)10(PPh3)2 and HRuCo3(CO)10(PPh3)2

A new ruthenium-rhodium mixed-metal cluster HRuRh₃(CO)₁₂ and its derivatives HRuRh₃(CO)₁₀(PPh₃)₂ and HRuCo₃(CO)₁₀(PPh₃)₂ have been synthesized and characterized. The following crystal and molecular structures are reported: HRuRh₃(CO)₁₂: monoclinic, space group P2₁/c, a 9.230(4), b 11.790(5), c 17.124(9) Å, β 91.29(4)°, Z = 4; HRuRh₃(CO)₁₀(PPh₃)₂·C₆H₁₄: triclinic, space group P$\text{1}$, a 11.777(2), b 14.079(2), c 17.010(2) Å, α 86.99(1), β 76.91(1), γ 72.49(1)°, Z = 2; HRuCo₃(CO)₁₀(PPh₃)₂·CH₂Cl₂: triclinic, space group P$\text{1}$, a 11.577(7), b 13.729(7), c 16.777(10) Å, α 81.39(4), β 77.84(5), γ 65.56°, Z = 2. The reaction between Rh(CO)₄^? and (Ru(CO)₃Cl₂)₂ tetrahydrofuran followed by acid treatment yields HRuRh₃(CO)₁₂ in high yield. Its structural analysis was complicated by a 80–20% packing disorder. More detailed structural data were obtained from the fully ordered structure of HRuRh₃(CO)₁₀(PPh₃)₂, which is closely related to HRuCo₃(CO)₁₀(PPh₃)₂ and HFeCo₃(CO)₁₀(PPh₃)₂. The phosphines are axially coordinated.     

Reactions of metal carbonyl cluster complexes with multidentate phosphine ligands; preparation of bis(diphenylphosphino)methane derivatives of the trinuclear complexes M3(CO)12 (M = Fe,Ru and Os) and the X-ray crystal structure of Os3(CO)9(μ-dppm)(η1-dppm) (dppm = Ph2pch2ppH2)

The reaction of bis(diphenylphosphino)methane (dppm) with Fe₃(CO)₁₂ gave the known complexes Fe(CO)₄ (dppm), Fe₂(CO)₇ (dppm), in addition to Fe₂CO)₅(dppm)₂. Two new dppm derivatives of Ru₃CO)₁₂, Ru₃(CO)₉(μ-dppm)(η¹-dppm) and Ru₃(CO)₆(dppm)₃ have been isolated and spectroscopically characterised. From the reaction of Os₃(CO)₁₂ with dppm, the derivatives Os₃(CO)₁₀(dppm), Os₃(CO)₉(μ-dppm)(η¹-dppm) and Os₃(CO)₈(dppm)₂ have been isolated. The crystal structure of Os₃(CO)₉(μ-dppm)(η¹-dppm) has been determined.     

Influence of Fe3(CO)12 on the interaction of Re2(CO)10 with hydroxylated alumina surface

The interaction of Re₂(CO)₁₀ and Fe₃(CO)₁₂, and that of Re₂Fe(CO)₁₄ with alumina were studied during thermal treatment by FT-IR spectroscopy. The interaction of Re₂Fe(CO)₁₄ with alumina results in the formation of Re-tricarbonyls as in the Re₂(CO)₁₀ + Fe₃(CO)₁₂/Al₂O₃ system, even at room temperature. In the view of this fact, the possibility of the action of reactive Fe-monocarbonyls [Fe(CO)₅, Fe(CO)₄] on the Re₂(CO)₁₀ with appearance of a Re₂Fe(CO)₁₄ as a transient intermediate on the support, cannot be excluded.     

The protonation and hydrogen transfer processes in alkene and alkyne derivatives of Os3 and H2Os3(CO)10

The complexes H₃O_s3(CO)₉CMe, H₂O_s3(CO)₁₀, H₂O_s3(CO)₉L (L = PEt₃, PPh₃ or AsPh₃), HO_s3(CO)₁₀CHC(H)Ph, and O_s3(CO)₁₀HC₂Me undergo protonation in acid to yield [H₄O_s3(CO)₉CMe]⁺ and [H₄O_s3(CO)₁₀]²⁺, [H₃O_s3(CO)₉L]⁺, [H₂O_s3(CO)₁₀CHC(H)Ph]⁺ and [HO_s3(CO)₁₀HC₂Me]⁺, respectively. The structure of these ions and their hydrido-ligand transfer reactions are described.