HRu3(CO)10(COCH3). A cluster with an oxygen-containing μ2-carbyne ligand; preparation,structure and fluxionality

The cluster HRu₃(CO)₁₀(COCH₃) has been prepared from Na[HRu₃(CO)₁₁] and [(CH₃)₃O]BF₄ in acetonitrile. The complex crystallises in the monoclinic space group P2₁/c, with cell dimensions a 7.937(2), b 16.880(9), c 14.074(3) Å, β 104.16(3)° and Z 4. The structure was solved by a combination of Patterson and Fourier techniques and refined by full-matrix least-squares to final residues of R = 0.031 and R_w = 0.035 for the 2529 unique intensities. The three ruthenium atoms define an approximately equilateral triangle with one edge bridged by both a μ₂-H and a μ₂-COCH₃ ligand. The fluxional behaviour of HRu₃(CO)₁₀-(COCH₃) has been studied by variable temperature ¹³C NMR spectroscopy. The spectra are indicative of several dynamic processes occurring in solution over the range ?100 to +90°C. The μ₂-COCH₃ species can be considered as a bridging three-electron donor and thus represents a μ₂-carbyne ligand.     

Synthesis,spectroscopic characterization and crystal and molecular structure of HRu3(OCN(CH3)2)(CO)10

Dimethylamine reacts with Ru₃(CO)₁₂ to produce the η²-hydrido-η-formamido cluster complex HRu(OCN(CH₃)₂)(CO)₁₀ (I). This formulation is consistent with spectroscopic features such as the absence of v(NH) in the infrared, the presence in the Raman of v(RuHRu) at 1400 cm^?1 (v(RuDRu) at 990 cm^?1) and indication in the ¹H NMR of diastereotopic methyl groups bonded to the nitrogen atom. Since these data could not lead to an unequivocal structure assignment a single crystal X-ray study at 115 K was undertaken. The complex crystallizes in the triclinic space group, P$\text{1}$ with cell dimensions; a 7.299(33) », b 9.5037(40) », c 13.7454(57) », α 91.876(34)°, β 96.387(34)°, γ 95.341(34)° and Z = 2. The structure was solved by a combination of Patterson and Fourier techniques and refined by full matrix least squares to a final R = 0.054 and R_ω = 0.074 for 3074 unique reflections. The three ruthenium atoms define a triangle of unequal sides with both the hydride and formamido groups bridging the longest edge; the formamido group is coordinated through the carbon and oxygen atoms. The edge of the ruthenium triangle bridged both by the hydrogen atom and the formamido group is 2.8755(15) »; the other two edges of the ruthenium triangle are observed to be 2.8319(15) and 2.8577(14) », respectively. In the formamido group the distance CO 1.287(9) » and CN 1.340(10) » reflect partial double bond charater in each bond consistent with observation of two chemically distinct methyl groups on the dinitrogen atom. The hydrogen atom bridging one edge of the ruthenium triangle is asymmetrically positioned at 1.73(9) » from the ruthenium atom bonded to the oxygen atom and 1.91(9) » from the ruthenium atom bonded to the carbon atom of the carboxamido group.     

Re4(CO)12[μ3-InRe(CO)5]4 und Re2(CO)8[μ-InRe(CO)5]2-cluster aus dem reaktionssystem In/Re2(CO)10 in xylol

The thermally stable solids Re₂(CO)₈[μ-InRe(CO)₅]₂ and Re₄(CO)₁₂[μ₃-InRe(CO)₅]₄ could be obtained by treatment of In with Re₂(CO)₁₀ in a bomb tube. A mechanism of the formation of the latter cluster from the first one is proposed. Compared with Re₂(CO)₈[μ-InRe(CO)₅]₂, Re₄(CO)₁₂[μ₃_InRe(CO)₅]₄ shows in polar solvents an unusual high stability, which can be explained by the higher coordination number of In with rhenium carbonyl ligands. Re₄(CO)₁₂-[μ₃-InRe(CO)₅]₄ dissolves monomerically in acetone, where as Re₂(CO)₈[μ-InRe(CO)₅]₂ dissociates yielding Re(CO)₅^? anions. Single-crystal X-ray analyses of Re₄(CO)₁₂[μ₃-InRe(CO)₅]₄ establish the metal skeleton. The central molecular fragment Re₄(CO)₁₂ contains a tetrahedral arrangement of four bonded Re atoms [ReRe 302.8 (5) pm]. The triangles of this fragment are capped with a μ₃-InRe(CO)₅ group each [InRe(terminal) 273.5 (7) pm; InRe (polyhedral) 281.8 (7) pm]. The bridging type of In atoms with the Re₄ tetrahedron and the metal skeleton was realized for the first time. By treating Re₄(CO)₁₂[μ₃-InRe(CO)₅]₄ with Br₂ the existence of Re(CO)₅ ligands could be proved by isolating BrRe(CO)₅.     

The reaction of Ru3(CO)12 and Os3(CO)12 with PH2Ph; the x-ray crystal structures of HRu3(CO)10(PHPh) and H2Ru3(CO)9(PPh)

Twelve new trinuclear complexes containing terminal PH₂Ph, edge-bridging PHPh and/or capping PPh ligands have been isolated from the reaction of M₃(CO)₁₂ (M = Ru or Os) with PH₂Ph in refluxing solvents. HRu₃(CO)₁₀(PHPh) (IIIa) crystallises in the monoclinic space group P2₁/c with a = 8.761(3), b = 11.402(4), c = 22.041(7) Å,β = 98.89(2)°, and Z = 4. The structure was solved by a combination of direct methods and Fourier difference techniques, and refined by blocked-cascade least squares to R = 0.027 for 3676 unique observed intensities. The X-ray analysis shows that one edge of the Ru₃ triangle is bridged by a hydride and the PHPh ligand, and that the phosphorus-bound hydrogen atom lies over the metal triangle and the phenyl group away from it. This provides an explanation for the ready formation of the capped species H₂Ru₃(CO)₉(PPh) (Va) on pyrolysis of the edge-bridged complex as opposed to the previously reported conversion of HOs₃(CO)₁₀(NHPh) to an orthometallated derivative under similar conditions. An X-ray analysis of H₂Ru₃(CO)₉-(PPh) (Va) confirms the capped geometry. the complex crystallises in the monoclinic space group P2₁/n with a = 9.323(4), b = 15.110(6), c = 45.267(15) Å,β = 91.84(3)°, and Z = 12. the structure was solved and refined using the same techniques as described previously. The final residual R is 0.061 for 4839 reflections. Some reactions of Va show that the phosphorous cap is difficult to displace and stabilises the molecule with respect to decomposition to non-cluster species.     

Cluster condensation reactions. The synthesis and crystal and molecular structure of Os6(CO)14(μ2-PPh2)2(μ3-S)3(μ4-S)

Thermal degradation of the cluster compound Os₃(CO)₈(PPh₂H)(μ₃-S)₂ (I) at 125°C leads to decarbonylation and formation of the new ligand bridged hexanuclear cluster Os₆(CO)₁₄(μ-PPh₂)₂(μ₃-S)₃(μ₄-S) (II) in 11% yield. Space Group: P$\text{1}$, No. 2, a 10.427(5), b 13.552(3), c 17.919(3) Å, α 84.87(2), β 75.41(3), γ 78.43(3)°, V 2399(2) ųZ = 2, _?calc 2.82 g cm^?3. The structure was solved by the heavy atom method and refined (3223 reflections) to the final residuals R = 0.042 and R_w = 0.036. The molecule consists of two sulfido bridged open triosmium clusters which are linked by a bridging sulfido ligand and a bridging diphenylphosphino ligand.     

Ligand substitution of FeRu2(CO)12 and Fe2Ru(CO)12 with tertiary phosphines and phosphites

Ligand substitution of the mixed-metal clusters FeRu₂(CO)₁₂ and Fe₂Ru(CO)₁₂ with triphenylphosphine and trimethylphosphite has been studied. Mono- and di-substituted derivatives have been synthesized and characterized structurally. The following crystal and molecular structures are reported: Fe₂Ru(CO)₁₁PPh₃: triclinic, space group P$\text{1}$, a 9.203(2), b 11.903(3), c 15.117(4) Å, α 81.54(2), β 87.28(2), γ 66.72(2)°, Z = 2; Fe₂Ru(CO)₁₁P(OMe)₃: orthorhombic, space group Pna2₁, a 17.220(5), b 14.572(4), c 8.708(6) Å, Z = 4, FeRu₂(CO)₁₁PPh₃: monoclinic, space group P2₁/n, a 11.435(3), b 16.034(5), c 16.642(4) Å, β 93.35(2)°, Z = 4; FeRu₂(CO)₁₀(PPh₃)₂: orthorhombic, space group Pccm, a 14.854(4), b 17.180(7), c 16.786(12) Å, Z = 4.Ligand substitution is found to occur preferentially at the ruthenium centers of the FeRu₂ and Fe₂Ru clusters. Monosubstitution causes expansion of both of the clusters while the overall geometry is practically unchanged. Disubstitution of FeRu₂(CO)₁₂ causes contraction of the cluster and leads to a formation of carbonyl bridges. The structural trends have been interpreted in terms of electronic and packing effects of ligand substitution. The X-ray structures of Fe₂Ru(CO)₁₂ and FeRu₂(CO)₁₂ are not known; the ligand substitution studies indicate that Fe₂Ru(CO)₁₂ has the same structure as Fe₃(CO)₁₂, and that FeRu₃(CO)₁₂ does not have a Ru₃(CO)₁₂ structure as postulated previously from the IR studies.     

Reactions of isonitriles with [Fe3(CO)12] and [Ru3(CO)12] monitored by electrospray mass spectrometry: structural characterisation of [Fe3(CO)10(CNPh)2] and [Ru4(CO)11(μ3-η-CNPh)2(CNPh)]

The reactions of [Fe₃(CO)₁₂] or [Ru₃(CO)₁₂] with RNC (R=Ph, C₆H₄OMe-p or CH₂SO₂C₆H₄Me-p) have been investigated using electrospray mass spectrometry. Species arising from substitution of up to six ligands were detected for [Fe₃(CO)₁₂], but the higher-substituted compounds were too unstable to be isolated. The crystal structure of [Fe₃(CO)₁₀(CNPh)₂] was determined at 150 and 298 K to show that both isonitrile ligands were trans to each other on the same Fe atom. For [Ru₃(CO)₁₂] substitution of up to three COs was found, together with the formation of higher-nuclearity clusters. [Ru₄(CO)₁₁(CNPh)₃] was structurally characterised and has a spiked-triangular Ru₄ core with two of the CNPh ligands coordinated in an unusual μ₃-η² mode.     

Reactions of tungsten and molybdenum propargyl complexes with Co2(CO)8, Co4(CO)12, and Cp2Mo2(CO)4. A crossover study of formation of (CO)3 Cp(CO)2

The nature of the protonation reaction of (

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o(CO)₃ (M = Mo, W; R = Me, Ph, p-MeC₆H₄) (2) (obtained from (CO)₃CpMCH₂CCR (1) and Co₂(CO)₈) to give (CO)₃ Cp(CO)₂ (3) was further investigated by a crossover experiment. Thus, reaction of an equimolar mixture of 2b (M = W, Cp = η⁵-C₅H₅, R = Ph) and 2e (M = W, Cp = η⁵-C₅H₄Me; R = p-MeC₆H₄) with CF₃COOH affords only 3b (same M, Cp, and R as 2b) and 3e (same M, Cp, and R as 2e) to show an intramolecular nature of this transformation. Reaction of (CO)₃CpWCH₂CCPh (1b) with Co₄(CO)₁₂ was also examined and found to yield 2b exclusively. Treatment of 1 with Cp₂Mo₂(CO)₄ at 0–5°C provides thermally sensitive compounds, possibly (CO)₂Cp

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oCp(CO)₂ (5), which decompose at room temperature to give Cp₂Mo₂(CO)₆ as the only isolated product.     

Topotactic insertion of lithium in the layered structure Li4VO(PO4)2: The tunnel structure Li5VO(PO4)2

A new V(III) lithium phosphate Li₅VO(PO₄)₂ has been synthesized by electrochemical insertion of lithium into Li₄VO(PO₄)₂. This phase, which crystallizes in the space group I4/mcm, exhibits a tunnel structure closely related to the layered structure of Li₄VO(PO₄)₂ and to the tunnel structure of VO(H₂PO₄)₂. The topotactic reactions that take place during lithium exchange and intercalation, starting from VO(H₂PO₄)₂ and going to the final phase Li₅VO(PO₄)₂ are explained on the basis of the flexible coordinations of V⁴⁺ and V³⁺ species. The electrochemical and magnetic properties of this new phase are also presented and explained on the basis of the structure dimensionality.     

CO hydration over catalysts prepared via supporting Fe3(CO)12 and (NEt4)2[Fe2Mn(CO)12] on oxide supports

A comparison of the properties of iron-containing catalysts prepared through carbonyl clusters Fe₃(CO)₁₂ and (NEt₄)₂[Fe₂Mn(CO)₁₂] and iron and manganese nitrates in CO hydration indicates that the addition of Mn incorporated in (NEt₄)₂[Fe₂Mn(CO)₁₂] decreases the methane yield and increases the portion of higher hydrocarbons.

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, Fe(CO)₁₂ (NEt₄)₂[Fe₂Mn(CO)₁₂] , CO. Mn (NEt₄)₂[Fe₂Mn(CO)₁₂] .

     

Synthesis and molecular structure of [Au3Ru4(μ3-H)(CO)12(PPh3)3]

The title compound can be prepared in good yield by heating either [Ru₄(μ-H)₄(CO)₁₂] or [Au₂Ru₄(μ₃-H)₂(CO)₁₂(PPh₃)₂] with [AuMe(PPh₃)] in toluene. The related compound [Au₃Ru₄(μ₃-H)(μ-dppm)(CO)₁₂(PPh₃)] has also been prepared. Both trigoldtetraruthenium clusters undergo dynamic behaviour in solution, involving intramolecular rearrangement of the metal core, as revealed by variable temperature NMR studies. The crystal structure of [Au₃Ru₄(μ₃-H)(CO)₁₂(PPh₃)₃] has been established by an X-ray diffraction study. The metal atom core comprises a trigonal bipyramidal AuRu₄ unit with two AuRu₂ faces capped by gold atoms.     

On the structure of H2Os3(CO)12

Infrared, far-infrared and Raman data are reported and discussed for H₂Os₃(CO)₁₂. ¹³C NMR studies for H₂Os₃(CO)₁₂ are also reported. These data are consistent with a linear arrangement of the three osmium atoms with terminal hydrides occupying equatorial positions on the end osmium atoms.     

Syntheses and structural studies on two cycloruthenapentadienyl complexes: [(CO)3RuC4(CH2OH)4]Ru(CO)3·H2O and [(CO)3RuC4(CH2CH2OH)2(C2H5)2]Ru(CO)3

Syntheses and single-crystal X-ray diffraction studies have been completed on two cycloruthenapentadienyl (CO)₆Ru₂L₂ derivatives, with L = CH₂OHC = CCH₂OH and C₂H₅C=CCH₂CH₂OH respectively. Crystal data are as follows: for [(CO)₃RuC₄(CH₂OH)₄]Ru(CO)₃·H₂O, P2₁/c, a 13.72(1), b 9.501(4), c 14.86(1) Å, β 101.10(6)°, R_w = 0.052 for 1911 reflections; for [(CO)₃RuC₄(CH₂CH₂OH)₂(C₂H₅)₂]Ru(CO)₃, P2₁/c, a 9.191(3), b 16.732(4), c 14.903(3) Å, β 113.61(4)°, R_w = 0.042 for 2865 reflections. Both compounds are built up from binuclear units, each unit being regarded as a Ru(CO)₃ fragment π-bonded to a cycloruthenapentadienyl ring. The molecular parameters are compared with those of known cyclometallapentadienyl complexes of transition metals. The presence of a semi-bridging CO group is discussed.     

Synthesis, structure and some reactions of (C5Me4hex)2Ru2(CO)4

The synthesis of the new cyclopentadiene, C₅Me₄(hex)H is described and its reaction with Ru₃(CO)₁₂ to yield (C₅Me₄hex)₂Ru₂(CO)₄ (hex = n-hexyl) is reported. The X-ray crystal structure of the dimer confirms the structure with bridging and terminal CO groups. Reactions of the dimer to yield (C₅Me₄hex)Ru(CO)₂X (X = Cl, Br, I) are reported. IR, NMR and mass spectra are reported for all new compounds. The solubility of the dimer is found to be 10 times greater than that for (C₅Me₅)₂Ru₂(CO)₄.     

Crystal and molecular structure of tris(3,3,4,4-tetramethyl- 3,4-dihydrodiazete)bis(tricarbonylchromium), (N2C2Me4)3[Cr(CO)3]2

Crystals of C₂₄H₃₆N₆O₆Cr₂ are monoclinic, a 15.380(3), b 13.965(2), c 14.459(3) Å, β 92.18(1)°; Z = 4; space group P2₁ with two independent molecules in the asymmetric unit. The crystal structure was determined from X-ray diffractometer data by direct methods and refined by least-squares methods to R = 0.066 for 2430 independent observed reflections. It consists of discrete molecules, in which each Cr atom is surrounded by three cis carbonyl groups and three cis nitrogen atoms of three 3,3,4,4-tetramethyl-1,2-diazetine ligands, in a deformed octahedral coordination. There is no evidence of intramolecular Cr ? Cr interaction.     

The synthesis of phosphine derivatives of [Fe4N(CO)12]: Crystal structures of [Fe4N(CO)9(NO)(PPh3)2], [HFe4N (CO)11)PPh3)] and [(PPh3)2N][Fe4N(CO)11(PMe2Ph)]

Phosphines react with butterfly tetranuelear nitrido-iron clusters, [Fe₄N(CO)₁₂]⁻ and [Fe₄N(CO)₁₁(NO)], to give mono- and di-substituted complexes. X-Ray analyses of the title compounds showed that the phosphine ligands are bound to the wing-tip atoms.     

Synthesis and reactivity of [(RRN)2PH]Fe(CO)4 complexes. X-ray crystal structure of [(Ph2N)2PH]Fe(CO)4

KHFe(CO)₄ reacts with tris(amino)phosphines by substitution at phosphorus leading to [bis(amino)phosphine]tetracarbonyliron complexes [(R¹R²N)₂PH]Fe(CO)₄. The X-ray structure has been determined for R¹=R²=Ph. Deprotonation of these complexes with KH affords stable potassium phosphidotetracarbonylferrates which can be alkylated or acylated at phosphorus.     

Pd(PBu 3 t ) Adducts of Os3(CO)12. Synthesis and Structures of Pd2Os3(CO)12(PBu 3 t )2 and Pd3Os3(CO)12 (PBu 3 t )3

Two new compounds Pd₂Os₃(CO)₁₂ , 13 and Pd₃Os₃(CO)₁₂ , 14 have been obtained from the reaction of with Os₃(CO)₁₂ at room temperature. The products were formed by the addition of two and three groups to the Os–Os bonds of Os₃(CO)₁₂. Compounds 13 and 14 interconvert between themselves by intermolecular exchange of the groups in solution. Compounds 13 and 14 have been characterized by single crystal X-ray diffraction analyses.Dedicated to Professor Brian F. G. Johnson on the occasion of his retirement – 2005.     

Improved syntheses of Ru(CO)2 (O3SCF3)2 (bidentate) complexes and their conversion into new [Ru(CO)2 (bidentate)2]2+ complexes

Reaction of the complexes Ru(CO)₂Cl₂L [L = 2,2′-bipyridyl (bpy) or 1,10-phenanthroline (phen)] with trifluoromethanesulphonic acid under carefully controlled conditions yields Ru[cis-(CO)₂] [cis-(O₃SCF₃)₂] (bidentate complexes. From reactions of the trifluoromethanesulphonates with the appropriate bidentate ligands, the new complexes [cis-Ru(CO)₂-L(L′)]²⁺ (L as above; L′ = 4,4′-dimethyl-2,2′-bipyridyl or 4,4′-diisopropyl-2,2′-bipyridyl) as well as the known [_cis-Ru(CO)₂L₂]²⁺ and [cis-Ru(CO)₂bpy(phen)]²⁺ have been prepared.