Synthesis and copolymerization reaction of a triosmium alkylidyne carbonyl cluster [Os3(μ-H)2(CO)9(μ3-CNC5H4-CH=CH2)]

A neutral triosmium alkylidyne carbonyl cluster containing the 4-vinylpyridine (4vpy) moiety [Os₃(µ-H)₂(CO)₉(µ₃-CNC₅H₄-CH=CH₂)] (1) has been prepared as red crystalline solids in good yield. Monomer (1) was copolymerized with styrene in the presence of ,'-azobis(isobutyronitrile) (AIBN) in chloroform at 60°C and a polymer-immobilized alkylidyne cluster of osmium was obtained. To compare the spectroscopic properties with the copolymers, a structurally similar repeating unit of the copolymers, [Os₃(µ-H)₂(CO)₉(µ-₃-CNC₅H₄-CH₂CH₃)I](2), has also been synthesized and characterized.     

Synthesis and structure of three isomeric cluster complexes (μ-H)Os3μ-O2CC5H4Mn(CO)3(PPh3)2(CO)8

The reaction of (μ-H)Os₃μ-O₂CC₅H₄Mn(CO)₃(CO)₁₀ with PPh₃ in the presence of Me₃NO gave mono- and disubstituted heterometallic complexes (μ-H)Os₃μ-O₂CC₅H₄Mn(CO)₃(PPh₃)(CO)₉ and (μ-H)Os₃μ-O₂CC₅H₄Mn(CO)₃ (PPh₃)₂(CO)₈. Crystal structure determination was performed for three isomeric cluster complexes (μ-H)Os₃μ-O₂CC₅H₄Mn(CO)₃(PPh₃)₂(CO)₈, which are both geometrical and conformational isomers differing in color. The geometrical isomerism is due to the attachment of the PPh₃ group at different vertices of the Os₃ triangle relative to the O₂CC₅H₄Mn(CO)₃ bridging ligand. The conform ational isomerism implies that the molecules have the same arrangement of ligands and differ only in the values of bond angles between the planar fragments of the clusters.     

Synthesis and structure of Os3(μ-H)3(CO)9(μ3-Sn)Os3(μ-H)(CO)10(PEt2Ph): The first osmium cluster containing a face-capping tin atom

Pyrolysis a the cluster Os₃(µ-H h (CO)₁₀ (SnMe2 H) produced an as yet unidentified purple duster, which upon reaction with PEt₂Ph at room temperature, gave essentially a quantitative yield of the cluster Os₃(µ-H)₃(CO)₉(µ₃-Sn) Os₃(µ-H)(CO)₁₀(PEt₂Ph), 4. The X-ray structure of 4 (as the toluene solvate) shows that it consists Or two Os, triangles linked through a µ₄-Sn unit, such that one of the Os₃ triangle is µ₃-bonded to the Sn atom (Os-Sn range 2.689(2)–2.707(2) Å) and the other is bonded via a single covalent bond (Os-Sn = 2.643(2) Å). The phosphine ligand occupies the equatorial site on a second osmium atom a be latter Os₃ moiety that is syn to the Sn atom; the unique bridging hydride ligarid is believed to occupy a site that Acis to both the P and Sn atoms. Crystallographic data for compound4. 0.5C₇H₈: space group,P ; ca= 11862(4) Å,b = 12.940(4) Å,c = 16.513(5) Å, =68.96(3),=80.60(3)°,=62.49(2).R=0.029, 4118 observed reflections.     

Synthesis and X-ray crystal structure of the electron-deficient metal carbonyl cluster [Os3(CO)5(μ3-H)(μ-H)(μ-PtBu2)2(μ-Ph2PCH2PPh2)]

The reaction of [Os₃(CO)₁₀(μ-dppm)] (1) with ^tBu₂PH in refluxing diglyme results in the electron-deficient metal cluster complex [Os₃(CO)₅(μ₃-H)(μ-P^tBu₂)₂(μ-dppm)] (2) (dppm = Ph₂PCH₂PPh₂) in good yields. The molecular structure of 2 has been established by a single crystal X-ray structure analysis. In contrast to the known homologue [Ru₃(μ-CO)(CO)₄(μ₃-H)(μ-H)(μ-P^tBu₂)₂(μ-dppm)] (3), no bridging carbonyl ligand was found in 2. The electronically unsaturated cluster 2 does not react with carbon monoxide under elevated pressure, therefore 2 seems to be coordinatively saturated by reason of the high steric demands of the phosphido ligands.     

Reactions of triosmium clusters Os3(CO)11(MeCN) and (μ-H)Os3(CO)10(μ-OH) withL-α-serine ethyl ester and ethanolamine

A series of novel chiral complexes with ,¹and ,² coordination of organic ligands were prepared by reactions of Os₃(CO)₁₁(MeCN) and (-H)Os₃(CO)₁₀(-OH) withL--serine ethyl ester and ethanolamine. The diastereomeric cluster complexes with serine ligands were separated by crystallization or chromatography. The structures of the compounds obtained were confirmed by¹H NMR and IR spectroscopy, mass-spectrometry, elemental analysis, and X-ray diffraction analysis.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 525–530, March, 1994.     

New triosmium–iridium clusters: Synthesis and molecular structure of [Os3Ir2(Cp1)2(μ-OH)(μ-CO)2(CO)8Cl] (1), [Os3IrCp1(μ-OH)(CO)10Cl] (2), [Os3IrCp1(μ-H)(μ-Cl)(η3,μ3-C5H2N(NH2)Br)(CO)9] (3) and [Os3IrCp1(μ-Cl)2(η2,μ3-C5H3N(NH)Br)(CO)7] (4)

The trinuclear osmium carbonyl cluster, [Os₃(CO)₁₀(MeCN)₂], is allowed to react with 1 equiv. of [IrCp¹Cl₂]₂ (Cp¹ = pentamethylcyclopentadiene) in refluxing dichloromethane to give two new osmium–iridium mixed-metal clusters, [Os₃Ir₂(Cp¹)₂(μ-OH)(μ-CO)₂(CO)₈Cl] (1) and [Os₃IrCp¹(μ-OH)(CO)₁₀Cl] (2), in moderate yields. In the presence of a pyridyl ligand, [C₅H₃N(NH₂)Br], however, the products isolated are different. Two osmium–iridium clusters with different coordination modes of the pyridyl ligand are afforded, [Os₃IrCp¹(μ-H)(μ-Cl)(η³,μ₃-C₅H₂N(NH₂)Br)(CO)₉] (3) and [Os₃IrCp¹(μ-Cl)₂ (η²,μ₃-C₅H₃N(NH)Br)(CO)₇] (4). All of the new compounds are characterized by conventional spectroscopic methods, and their structures are determined by single-crystal X-ray diffraction analysis.     

Synthesis and structures of complexes Os3(μ-H)2(CO)7(μ-RC5H3N){μ3-Ph2PCH2P(C6H4)Ph} (R = H, Me) with ortho-metalated pyridine ligands. The revised structure of the triosmium cluster ”Os3(μ-H)2(CO)7(μ-C6H4){μ3-Ph2PCH2P(C6H4)Ph}”

The structure of the previously synthesized triosmium cluster was revised. The structure Os₃(μ-H)₂(CO)₇(μ-C₆H₄){μ₃-Ph₂PCH₂P(C₆H₄)Ph} suggested earlier was not confirmed. The cluster has the composition Os₃(μ-H)₂(CO)₇(μ-C₅H₄N){μ₃-Ph₂PCH₂P(C₆H₄)Ph} and contains the ortho-metalated pyridine ligand. The X-ray diffraction study of the complex Os₃(μ-H)₂(CO)₇(μ-MeC₅H₃N){μ₃-Ph₂PCH₂P(C₆H₄)Ph} containing the ortho-metalated 4-methylpyridine ligand made it possible to distinguish between the C and N atoms of the pyridine ligands in the resulting triosmium clusters.     

Photochemical reaction of the heterometallic complex (μ-H)Os3{μ-O2CC5H4Mn(CO)3}(CO)10 with triphenylphosphine

Photolysis of the heterometallic complex (μ-H)Os₃{μ-O₂CC₅H₄Mn(CO)₃}(CO)₁₀ together with PPh₃ results in replacement of the CO groups by PPh₃ both at the Mn atom and in the Os₃ metallocycle to afford the complexes (μ-H)Os₃{μ-O₂CC₅H₄Mn(CO)₂PPh₃}(CO)₁₀, (μ-H)Os₃{μ-O₂CC₅H₄Mn(CO)₃}(CO)₉}(CO)₉PPh₃, and (μ-H)Os₃{μ-O₂CC₅H₄Mn(CO)₂PPh₃}(CO)₉PPh₃ (two isomers). The reaction is also accompanied by the partial removal of the Mn(CO)₃ group followed by the protonation of the cyclopentadienyl group and formation of triosmium clusters (μ-H)Os₃(μ-O₂CC₅H₄R}(CO)₁₀ (R=H, Et). Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 746–751, April, 2000.     

The reaction of [PPN][(μ2-H)Os3(CO)10(μ2-CO)] with EPh3 (E=P or As) to form the intermediate [PPN][Os3(CO)9(ν2-CHO)(EPh3)]

The anion, [(₂-H)Os₃(CO)₁₀(₂-CO)]^–, reacts with the donor ligand EPh₃ (E=P or As) to produce, as an intermediate in the reaction to the substituted anion [(₂-H)Os₃(CO)₉(₂-CO)(EPh₃)]^–, a moderately stable formyl derivative which we tentatively formulate as [Os₃(CO)₉(²-CHO)(EPh₃)]^–.     

Reactions of the unsaturated anion [Re3(μ-H)4(CO)10]− with phosphines. Synthesis of the anions [Re3(μ-H)2(CO)10(PR3)2]−, and crystal structure of [NEt4][Re3(μ-H)2(CO)10(PPh3)2]

The reaction of the unsaturated cluster anion [Re₃(μ-H)₄(CO)₁₀]⁻ with tertiary phosphines at room temperature results in the substitution of two hydride ligands (eliminated as H₂) by two PR₃ ligands, leading to saturated [Re₃(μ-H)₂(CO)₁₀-(PR₃)₂]⁻ compounds. A single crystal X-ray diffraction study of the PPh₃ derivative revealed that the two phosphines occupy non-equivalent equatorial coordination sites on the triangular cluster. The rate of the reaction greatly increases with increase of the basicity of the phosphine.     

Synthesis and structural characterization of [Au2Pd14(μ3-CO)7(μ2-CO)2(PMe3)11](PF6)2—An icosahedrally-based high nuclearity mixed metal cluster

[Au₂Pd₁₄(₃-CO)₇(₂-CO)₂(PMe₃)₁₁](PF₆)₂ has been synthesized from [Pd₈(CO)₈(PMe₃)₇] and AuCl(PCy₃) in the presence of TIPF₆. It has been characterised on the basis of mass spectrometry, infrared and NMR spectroscopy, and a single crystal X-ray diffraction study. The structure is based on a palladium-centered Au₂Pd₁₁ icosahedron which shares an edge with a Pd₅ trigonal bipyramid.This paper is dedicated to Larry Dahl on his 65th Birthday—his enthusiasm and achievements in cluster chemistry have inspired us all for more than 30 years.     

Synthesis and the crystal structure of the triosmium cluster with the μ-dehydrobenzene ligand,Os3(μ-H)2(CO)7(μ-C6H4){μ3-Ph2PCH2P(C6H4)Ph}

The Os₃(-H)₂(CO)₇(-C₆H₄){₃-Ph₂PCH₂P(C₆H₄)Ph} complex, which was isolated from the products of thermolysis of Os₃(CO)₁₀(-dppm) (dppm is Ph₂PCH₂PPh₂) in toluene, was characterized by X-ray diffraction analysis. Protonation of the resulting complex with trifluoroacetic acid afforded the cationic complex [Os₃(-H)₃(CO)₇(-C₆H₄){₃-Ph₂PCH₂P(C₆H₄)Ph}]⁺.     

Protonation and acylation of the heterometallic complexes (μ-H)Os3(μ-O2CC5H4FeCp)(CO)10 and Fe{(μ-O2CC5H4)(μ-H)Os3(CO)10}2

The reactions of the heterometallic complexes (-H)Os₃(-O₂CC₅H₄FeCp)(CO)₁₀ (1) and Fe{(-O₂CC₅H₄)(-H)Os₃(CO)₁₀}₂ (2) with CF₃COOH, CF₃SO₃H, and AcCl were studied. The reaction of 1 with CF₃COOH involves interaction with the Cp ligands, protonation of the O atom of the bridging carboxylate group, and oxidative degradation of the complex. At low concentrations, CF₃SO₃H protonates the O atom of the bridging carboxylate group, while at high concentrations, degradation of the complex takes place. The reaction of complex 2with either CF₃COOH or low concentrations of CF₃SO₃H results in successive elimination of two [(-H)Os₃(CO)₁₀] cluster fragments due to protonation of the O atoms of the carboxylate groups. In the case of high CF₃SO₃H concentrations, the Os—Os bonds of both cluster fragments of 2 are also protonated to give the [Fe{(-O₂CC₅H₄)(-H)₂Os₃(CO)₁₀}₂]²⁺ dication. The Friedel—Crafts acylation of 1 takes place only when a large excess of AcCl and AlCl₃ is used to give two new complexes, (-H)Os₃(-O₂CC₅H₄FeC₅H₄C(O)CH₃)(CO)₁₀ and (-H)Os₃(-O₂CC₅H₃C(O)CH₃FeCp)(CO)₁₀ in a 2 : 1 ratio.     

Fe3(CO)8[P[SC6H5)Cl2](μ3-S)2的合成和晶体结构

The title compound Fe_3(CO)_8 (P(SC_6H_5) Cl_2) (μ_3′-S)_2 was synthesised by reacting Fe_3(CO)_9 (μ_3-S)_2 with P (SC_6H_5) Cl_2. The crystal and molecular structure of the title compound has been determined by single crystal diffraction method. Crystal data: triclinic, space group P1, with a=0.7571(1), b=0.9097(1), c=1.7706(2) nm, α=95.03(1), β=101.79(1), γ=105.73(1)°, V =1.1359 nm, Z=2, Dc=1.935 g·cm~(-3). The structure was solved by direct method and difference Fourier synthesis, and refined by full-matrix least-squares with anisotropic thermal paramaters for non-hydrogen atoms, using 3724 observed reflections withI≥3σ(I). The final residual factor R=0.025, R_W=0.028.Fe_(CO)_8(P(SC_6H_5)Cl_2)(μ_3-s)_2 has a face-bridged 4e donors and the monosubstituted ligand is on the apical Fe atom.     

Synthesis and protonation of an OS3(μ-H)(CO)10(μ-σ,η2-C≡CCMe2OMe) cluster

Triosmium cluster Os₃(-H)(CO)₁₀(--²-CCC Me₂OMe) (1) was obtained by treating OS₃(-H)(-Cl)(CO)₁₀ with LiCCCMe₂OMe. The reaction of cluster1 with HBF₄ · Et₂O at –60 °C leads to the cationic complex [Os₃(-H)(CO)₁₀(-,,²-C=C=C Me₂)]⁺BF₄ ^– (2) with an allenylidene ligand. The^s1H and¹³C NMR spectra of complex2 reveal the temperature dependence caused by migration of hydrocarbon and carbonyl ligands. Thermodynamic parameters were obtained for be exchange process of the allenylidene ligand.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp, 2990–2992, December, 1996.     

The synthesis and reactivity of the heptanuclear dianion [Os7(CO)20]2− including the synthesis and structural characterizations of the compounds [Os7(CO)20(AuPEt)3 2] and [Os8(CO)20(η6-C6H6]

Reduction of the heptaosmium cluster [Os₇(CO)₂₁] With [Et₄N][NH₄) gives the cluster dianion [Os₇(CO)₂₀]^2–,1, in high yield. The reaction of the dianion with [AuPR ₃Cl] (R=Et or Ph) in the presence of TlPF₆ forms [Os₇((CO)₂₀(AuPR ₃)₂] [R=Et (2a);R = Ph(2b)] in 80% yield, while the corresponding reaction with (Os(C₆H₆)(CH₃CN)₃]²⁺ gives [Os₈(CO)₂₀ ( ⁶-C₆H₆)] (3) in reasonable yield (ca. 30%). The dianion,1, and the clusters2 and3 have been fully characterized by bout spectroscopic and crystallographic methods. The crystal structure of the [Ph₄P]⁺ salt of1 shows that the metals in the anion adopt a capped octahedral geometry, with all twenty carbonyl ligands in terminal sites. The metal core geometry in2a is best described as a tricapped octahedron, and is based on the structure of the dianion1 with two adjacent octahedral faces capped by the Au atoms of the two AuPEt₃ groups. In a similar fashion, the geometry of3 is related to that of1 with the addition of an Os(C₆H₆) unit capped to a triangular face, to give a bicapped octahedral framework.     

Co-ordinatively unsaturated metal cluster compounds: Facile reactivity of the phosphinidene-capped phosphido-bridged triruthenium cluster [Ru3(μ3-PPh)(μ2-PPh2)2(CO)7]

The purple, phosphinidene-capped, phosphido-bridged triruthenium cluster [Ru₃(μ₃-PPh)(μ₂-PPh₂)₂(CO)₇] reacts readily with carbon monoxide, trimethylphosphite, sodium borohydride and diphenylacetylene under mild conditions to afford product mixtures from which [Ru₃(μ-PPh)(μ₂-PPh₂)₂(CO)_7+n] (n = 1, 2 or 3), [Ru₃(μ₃-PPh)(μ₂-PPh₂)₂(CO)₆{P(OMe)₃}], [Ru₃(μ₃-η³-PhPCPhCPh)(μ₂-PPh₂)₂(CO)₆], respectively, can be isolated. The structure of [Ru₃(μ₃-PPh)(μ₂-PPh₂)₂(CO)₆{P(OMe)₃}] has been established X-ray crystallographically.     

Reactions of Unsaturated Quinoline Triosmium Clusters [Os3(CO)9(μ3-η2-C9H5(4-R)N)(μ-H)] (R=Me or H) with Tetramethylthiourea: X-ray Structures of [Os3(CO)8(μ-η2-C9H5(4-Me)N)(η2-SC(NMe2NCH2Me)(μ-H)2] and [Os3(CO)9(μ-η2-C9H6N)(η1-SC(NMe2)2)(μ-H)]

Treatment of the electronically unsaturated 4-methylquinoline triosmium cluster $[\hbox{Os}_{3}\hbox{(CO)}_{9}(\upmu_3\hbox{-}\upeta^{2}\hbox{-}\hbox{C}_{9}\hbox{H}_{5} \hbox{(4-Me)N})(\upmu\hbox{-H})]$ (1) with tetramethylthiourea in refluxing cyclohexane at 81°C gave $[\hbox{Os}_{3}\hbox{(CO)}_{8}(\upmu\hbox{-}\upeta^{2}\hbox{-C}_{9}\hbox{H}_{5} \hbox{(4-Me)N})(\upeta^2\hbox{-SC}(\hbox{NMe}_2\hbox{NCH}_2\hbox{Me})(\upmu \hbox{-H})_2]$ (2) and $[\hbox{Os}_{3}\hbox{(CO)}_{9}(\upmu\hbox{-}\upeta^{2}\hbox{-C}_{9}\hbox{H}_{5}\hbox{(4-Me)N})(\upeta^1\hbox{-SC}(\hbox{NMe}_2)_2)(\upmu\hbox{-H})]$ (3). In contrast, a similar reaction of the corresponding quinoline compound $[\hbox{Os}_{3}\hbox{(CO)}_{9}(\upmu_{3}\hbox{-}\upeta^{2}\hbox{-C}_{9}\hbox{H}_{6}\hbox{N})(\upmu\hbox{-H})]$ (4) with tetramethylthiourea afforded $[\hbox{Os}_{3}\hbox{(CO)}_{9}(\upmu\hbox{-}\upeta^{2}\hbox{-C}_{9}\hbox{H}_{6}\hbox{N})(\upeta^{1}\hbox{-SC(NMe}_{2})_{2})(\upmu\hbox{-H)}]$ (5) as the only product. Compound 2 contains a cyclometallated tetramethylthiourea ligand which is chelating at the rear osmium atom and a quinolyl ligand coordinated to the Os₃ triangle via the nitrogen lone pair and the C(8) atom of the carbocyclic ring. In 3 and 5, the tetramethylthiourea ligand is coordinated at an equatorial site of the osmium atom, which is also bound to the carbon atom of the quinolyl ligand. Compounds 3 and 5 react with PPh₃ at room temperature to give the previously reported phosphine substituted products $[\hbox{Os}_{3}\hbox{(CO)}_{9}(\upmu \hbox{-}\upeta^{2}\hbox{-C}_{9}\hbox{H}_{5}\hbox{(4-Me)N)(PPh}_{3})(\upmu\hbox{-H)}]$ (6) and $[\hbox{Os}_{3}\hbox{(CO}_{9}(\upmu \hbox{-}\upeta^{2}\hbox{-C}_{9}\hbox{H}_{6}\hbox{N)(PPh}_{3})(\upmu\hbox{-H)}]$ (7) by the displacement of the tetramethylthiourea ligand.