Chlorine-atom abstraction and cluster fragmentation in the reaction of H3Re3(CO)10(MeCN)2 with the diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd): X-ray diffraction structure of fac-ClRe(CO)3(bpcd)

Treatment of the activated trirhenium cluster H₃Re₃(CO)₁₀(MeCN)₂ with the diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) in CH₂Cl₂ does not afford the expected cluster product H₃Re₃(CO)₁₀(bpcd) but rather the mononuclear complex fac-ClRe(CO)₃(bpcd). The identity of fac-ClRe(CO)₃(bpcd) was determined in solution by IR and NMR (¹H and ³¹P) spectroscopies and the solid-state structure was established by X-ray diffraction analysis. fac-ClRe(CO)₃(bpcd) crystallizes in the triclinic space P-1, a = 9.958(2) Å, b = 11.991(3) Å, c = 13.676(3) Å, α = 73.230(4)°, β = 73.806(4)°, γ = 77.409(4)°, V = 1484.6(6) ų, Z = 2, and d _calc = 1.723 Mg/m³; R = 0.0367, R _w  = 0.0857 for 4253 reflections with I > 2σ(l).     

Ligand-induced polyhedral opening in the mixed-metal cluster MeCCo2NiCp(CO)6 by 4,5-Bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd): X-ray structure of Co2NiCp(CO)4[μ2,η2,η1-C(Me)C=C(PPh2)C(O)CH2C(O)](μ2-PPh2)

The mixed-metal cluster MeCCo₂NiCp(CO)₆ (1) reacts with the diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) in refluxing CH₂Cl₂ to afford the disubstituted cluster MeCCo₂NiCp(CO)₄(bpcd) (2), which exists as a 1:1 mixture of bridging and chelating bpcd isomers. VT ³¹P NMR spectroscopy confirms that the two bpcd isomers do not interconvert in solution over the temperature range of 182–298 K. Thermolysis of cluster 2 leads to bpcd/cluster activation and formation of the phosphido-bridged cluster Co₂NiCp(CO)₄[μ₂,η²,η¹-C(Me)C=C(PPh₂)C(O)CH₂C(O)](μ₂-PPh₂) (3). The ligand-induced polyhedral expansion that accompanies the formation of the title cluster was established by X-ray diffraction analysis. Co₂NiCp(CO)₄[μ₂,η²,η¹-C(Me)C=C(PPh₂)C(O)CH₂C(O)](μ₂-PPh₂) crystallizes in the triclinic space group P-1, a=9.679(2), b=11.691(2), c=16.653(3) ?, α=85.849(3)°, β=85.456(4)°, γ=66.453(3)°, V=1720.3(6) A³, Z=2, D _cacl=1.632 Mg/m³; R=0.0874, R _w=0.1998 for 7053 observed reflections with I > 2σ(I).     

Syntheses and X-ray structures of the bridging and chelating isomers of Os3(CO)10(dmpe)

The substitution chemistry of the activated clusters Os₃(CO)₁₀(MeCN)₂ (1) and Os₃(CO)₁₀(1,5-cod) (2) has been investigated with the bidentate ligand 1,2-bis(dimethylphosphino)ethane (dmpe). Both starting clusters react rapidly with dmpe at room temperature to give the corresponding substitution product Os₃(CO)₁₀(dmpe) (3), whose isomeric composition is shown to depend on the nature of the starting cluster. Whereas the bridged cluster 1,2-Os₃(CO)₁₀(dmpe) (3b) was formed almost exclusively upon reaction with Os₃(CO)₁₀(MeCN)₂, a near statistical mixture of bridging (3b) and chelating (3c) isomers of Os₃(CO)₁₀(dmpe) was found in the reaction employing Os₃(CO)₁₀(1,5-cod). Both dmpe isomers have been characterized in solution by 3iP NMR spectroscopy and their solid-state structures established by X-ray crystallography. The bridged cluster 1,2-Os₃(CO)₁₀(dmpe) crystallizes in the monoclinic space group P2₁/n, a = 9.867(2) Å, b = 17.081(3) Å, c = 14.198(2) Å, β = 95.902(3)°, V = 2380.4(6) ų, Z = 4, and d _calc = 2.793 Mg/m³; R = 0.0435, R _w = 0.0466 for 3519 reflections with I > 2σ(I). The chelated cluster 1,1-Os₃(CO)₁₀(dmpe) crystallizes in the orthorhombic space group C222(1), a = 8.329(3) Å, b = 19.028(6) Å, c = 15.008(5) Å, V = 2379(1) ų, Z = 4, and d _calc = 2.795 Mg/m³; R = 0.0390, R _w = 0.0718 for 2360 reflections with I > 2σ(I).     

Ligand substitution in the halo-bridged diruthenium compound [Ru(CO)3Cl2]2 by 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd). Synthesis, spectral properties, and X-ray diffraction structures of cis(CO), trans(Cl)-RuCl2(CO)2 (bpcd) and cis(CO)-RuCl[C(O)Et](CO)2(bpcd)

The reaction between 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) and the chlorobridged diruthenium complex [Ru(CO)₃Cl₂]₂ (1) proceeds readily at room temperature in CH₂Cl₂ to give the new ruthenium compounds cis(CO),trans(Cl)-RuCl₂(CO)₂(bpcd) (2) and cis(CO)-RuCl[C(O)Et](CO)₂(bpcd) (3) as the major and minor products, respectively. Compound 2 was isolated and fully characterized in solution, and the molecular structure was established by X-ray diffraction analysis. cis(CO),trans(Cl)-RuCl₂(CO)₂(bpcd) crystallizes in the triclinic space P-1, a = 9.931(5) Å, b = 12.093(7) Å, c = 13.529(7) Å, α = 72.886(9)°, β = 74.739(9)°, γ = 76.851(9)°, V = 1478.2(1) ų, Z = 2, and d _calc = 1.556 mg/m³; R = 0.0841, R _w = 0.1880 for 4137 reflections with I > 2σ(I). The chlorine atoms in 2 adopt a trans geometry at the octahedral ruthenium center, with the two CO groups exhibiting a cis orientation and trans to the bpcd ligand. cis(CO)–RuCl[C(O)Et](CO)₂(bpcd) crystallizes as two independent molecules in the unit cell in the triclinic space P-1, a = 9.941(2) Å, b = 14.867(2) Å, c = 22.414(3) Å, α = 80.257(3)°, β = 84.796(2)°, γ = 75.207(3)°, V = 3152.6(8) ų, Z = 4, and d _calc = 1.504 mg/m³; R = 0.0428, R _w = 0.0962 for 8242 reflections with I > 2σ(I). The two CO groups are situated cis to each and are opposite to chlorine and phosphine moieties. The production of the minor propionyl compound 3 is discussed with respect to the trace amount of EtOH that is present in the CHCl₃ solvent that is used in the preparation of [Ru(CO)₃Cl₂]₂.     

Diphosphine ligand substitution in H4Ru4(CO)12: X-ray diffraction structures and reactivity studies of the cluster compounds H4Ru4(CO)10(P–P) [where P–P–(Z)–Ph2PCH–CHPPh2, bpcd]

The tetraruthenium cluster H₄Ru₄(CO)₁₂ (1) has been studied for its reactivity with the unsaturated diphosphine ligands (Z)–Ph₂PCH–CHPPh₂ and 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) under thermal, near-UV photolysis, and Me₃NO-assisted activation. All three cluster activation methods promote loss of CO and furnish the anticipated substitution products H₄Ru₄(CO)₁₀[(Z)–Ph₂PCH–CHPPh₂] (2) and H₄Ru₄(CO)₁₀(bpcd) (3) that possess a chelating diphosphine ligand. Clusters 2 and 3 have been characterized in solution by IR and NMR spectroscopies, and these data are discussed with respect to the crystallographically determined structure for both new cluster compounds. The ³¹P NMR spectral data and the solid-state structures confirm the presence of a chelating diphosphine ligand in clusters 2 and 3. Cluster 2 crystallizes in the monoclinic space P2₁/c, a=11.768(6) ?, b=18.521(9) ?, c=20.48(1) ?, β=102.291(8)°, V=4361(4) A³, Z=4, and d _calc=1.726 Mg/m³; R=0.0225, R _w=0.0491 for 6798 reflections with I > 2σ(I). The four bridging hydrides were located in H₄Ru₄(CO)₁₀[(Z)–Ph₂PCH–CHPPh₂] and their adopted positions are discussed relative to the solution ¹H NMR spectrum. H₄Ru₄(CO)₁₀(bpcd) crystallizes in the orthorhombic space Pbca, a=19.072(3) ?, b=20.169(3) ?, c=22.774(3) ?, V=8760(2) A³, Z=8, and d _calc=1.870 Mg/m³; R=0.0428, R _w=0.0896 for 10296 reflections with I > 2σ(I). Sealed NMR tubes containing clusters 2 and 3 were found to be exceeding stable towards near-UV light and temperatures up to ca. 125 °C. The surprisingly robust behavior of 2 and 3 is contrasted with the related cluster Ru₃(CO)₁₀(bpcd) that undergoes fragmentation to the donor-acceptor compound Ru₂(CO)₆(bpcd) and the phosphido-bridged compound Ru₂(CO)₆(μ–PPh₂)[μ–C–C(PPh₂)C(O)CH₂C(O)] under mild conditions. The electrochemical properties of each substituted cluster have been investigated by cyclic voltammetry, and our findings are discussed with respect to the reported electrochemical data on the parent cluster H₄Ru₄(CO)₁₂.

Knoevenagel condensation of the diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopentene-1,3-dione with 9-anthracenecarboxaldehyde: Synthesis of the second-generation ligand 2-(anthracen-9-ylidene)-4,5-bis(diphenylphosphino)-4-cyclopentene-1,3-dione

The Knoevenangel condensation between 9-anthracenecarboxaldehyde and the diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopentene-1,3-dione (bpcd) takes place rapidly in CH₂Cl₂/MeOH solution in the presence of molecular sieves (4 ?) to produce the functionalized ligand 2-(anthracen-9-ylidene)-4,5-bis(diphenylphosphino)-4-cyclopentene-1,3-dione. The title compound has been isolated and characterized in solution by IR, NMR, and UV-vis spectroscopies, and the solid-state structure has been established by X-ray diffraction analysis. 2-(anthracen-9-ylidene)-4,5-bis(diphenylphosphino)-4-cyclopentene-1,3-dione crystallizes in the triclinic space group P−1, a=10.227(2) ?, b=13.865(2) ?, c=15.905(2) ?, α=112.157(2)°, β=101.424(2)°, γ=100.065(3)°, V=1968.5(5) ?³, Z=2, and d _calc=1.101 Mg/m³; R=0.0873, R _w=0.2604 for 7452 reflections with I>2σ(I). The cyclic voltammetric behavior for 2-(anthracen-9-ylidene)-4,5-bis(diphenylphosphino)-4-cyclopentene-1,3-dione has been studied, and the observed redox data and results from extended Hückel MO calculations are discussed relative to the parent ligand bpcd.

Synthesis and crystal structures of two new complexes [M(OH2)(HDPA)2]·3H2O (M = Mn, Co)

Two new transition metal complexes of [M(OH₂)(HDPA)₂]·3H₂O (M=Mn(1); M=Co(2)) (H₂DPA, 2,6-pyridine-dicarboxylic acid) have been prepared at room temperature from the reaction of MCl₂·6H₂O (M=Mn or Co) and H₂DPA in the mixed solvent of H₂O and EtOH in the presence of piperazine, and were characterized by X-ray analysis, elemental analysis. X-ray analysis reveals that the coordination geometries of Mn²⁺ and Co²⁺ are of octahedron and severely distorted square-based pyramid, respectively. Crystal data: [Mn(OH₂)(HDPA)₂]·3H₂O (1), Mr=459.23, monoclinic, P2(1)/n, a=7.0056(3), b=(23.8125(12), c=10.7444(3) ?, β=99.834(2)°, Z=4, V=1766.28(13) ?³, R ₁=0.0586, wR ₂=0.1448 [I>2σ(I)]; Co(OH₂)(HDPA)₂]·3H₂O (2), Mr=463.22, monoclinic, P2(1)/n, a=7.0014(2), b=23.8346(7), c=10.7212(4) ?, β=99.8540(10)°, Z=4, V=1762.71(10) ?³, R ₁=0.0474, wR ₂=0.1366 [I>2σ(I)].     

Trimethylamine-N-oxide induced disproportionation of Re2(CO)10: Synthesis and X-ray crystal structure of [fac-Re(CO)3(ONMe3)3] [ReO4]

An attempted synthesis of [Re(CO₃) (-OH)]₄,1, by reacting Re₂(CO)₁₀ with an excess of NMe₃O in THF resulted instead in isolation of a disproportionation product, [fac-Re(CO)₃(ONMe₃)₃][ReO₄],2. The structure of2 was determined via X-ray crystallography: tri-clinic,P1^¯,a=9.499(5),b=9.841(2),c=13.448(2)Å,=109.92(2),=106.89(3), =93.15(4)°,D _calc=2.22 g^–3 andZ=2. Least-squares refinement based on 1606 observed (I>3(I)) reflections gave final values ofR=0.040 andR _w=0.047. The cation is a distorted octahedron that exhibits several structural manifestations of steric crowding among the bulky NMe₃O ligands.     

CO substitution in Ru3(CO)12 by 2,3-bis(diphenylphosphino)-N-phenyl-maleimide (bppm). X-ray diffraction structure of Ru2(CO)6(bppm)

The cluster Ru₃(CO)₁₂ reacts with the diphosphine ligand 2,3-bis(diphenylphosphino)-N-phenyl-maleimide (bppm) in toluene solution at 100C by fragmentation to give a 2:1 mixture of the donor–acceptor complex Ru₂(CO)₆(-bppm) and the phosphido-bridged species Ru₂(CO)₆ , respectively. The new diruthenium compounds have been isolated by chromatography and characterized in solution by IR and NMR (¹H and ³¹P) spectroscopies, in addition to X-ray diffraction analysis in the case of Ru₂(CO)₆( ₂ -bppm). Ru₂(CO)₆( ₂ -bppm), which exists as two crystallographically independent molecules in the unit cell, crystallizes in the orthorhombic space group Pbca, a = 18.8441(9), b = 21.352(2), c = 36.510(2) Å, V = 14,690(1) ų, z = 16, D _calc = 1.649 g/cm³; R = 0.0356, and R _w = 0.0812 for 17732 observed reflections. The reactivity of the bis(diphenylphosphino)-N-phenyl-maleimide ligand with Ru₃(CO)₁₂ under thermolysis conditions is contrasted with the related diphosphine ligands 2,3-bis(diphenylphosphino)maleic anhydride (bma) and 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd).     

Crystal structure of cis-[Rh(biq)2Cl2]Cl·3H2O: Solid-state characterization and crystal packing analysis

The title compound, cis-[Rh(biq)₂Cl₂]Cl·3H₂O (biq = 2,2′-biquinoline) crystallized in the monoclinic space group P2 ₁ /n with a = 11.231(2) Å, b = 20.895(4) Å, c = 14.081(3) Å, β = 94.76(3)°, V = 3293.0(11) ų, D _c = 1.565 g cm⁻³, μ = 0.806 mm⁻¹, F(000) = 1576 and Z = 4. It contains a monomeric [Rh(biq)₂Cl₂]⁺ cation, a chloride ion and three molecules of H₂O. The rhodium(III) ion is hexa coordinated forming a distorted octahedral arrangement. The mean Rh(III)–N distance for the four Rh(III)–N bonds is 2.0625 Å. The two chloride atoms are bonded in a cis configuration [Rh(III)–Cl bond distances are 2.329(3) and 2.341(4) Å]. The structure shows a curling stacks of cationic complexes interacting via offset-face-to-face (OFF) π–π aryl interaction motif. Water molecules and chloride ions are hydrogen bonded (H₂O···H–OH and Cl···H–OH) and links the curling stacks by hydrogen bonding via Rh–Cl···H–OH interactions.     

Crystal structure of Co4(CO)10S2 and Co4(CO)10Se2; v(CO) vibrations of a model cluster molecule: Co4(CO)10S2

The crystal structure of Co₄(CO)₁₀S₂ has been redetermined and that of Co₄(CO)₁₀Se₂ obtained by X-ray analysis. The compounds are monoclinic and isomorphous, space groupP2₁/n,Z=2, with (S compound)a=10.42(2)Å,b=6.794(1)Å,c=12.421(2)Å,=97.27(1) and (Se compound)a=10.110(2)Å,b=6.747(2)Å,c=12.592(4)Å,=96.37(2); finalR(S)=0.029,R _w =0.032 for 1414 reflections and finalR (Se)=0.052,R _w =0.054 for 1264 reflections. The molecules, which lie on a crystallographic center of symmetry, consist of a rectangle with Co atoms at the corners, each face of the rectangle being capped by a chalcogen atom. Each Co atom is bonded to two terminal CO groups; there are two bridging CO groups, one on each member of a pair of opposite sides of the rectangle. The vibrational spectra of the sulfur compound are considered in detail. A study of the crystal structure, and recognition of an approximate spectroscopic space group, are shown to be essential for an understanding of thev(CO) infrared spectrum of polycrystalline Co₄(CO)₁₀S₂. In this molecule, intramolecular vibrational coupling in the crystal leads to extensive modifications of the infrared-activev(CO) molecular coordinates.     

Synthesis and characterization of Bis(μ-sulfido)bis[{O,O-dimethyldithiophosphato}oxomolybdenum(V)]. Crystal structure of Mo2O2(Φ-S2)[S2P(OMe)2]2.C6H6

Bis(μ-sulfido)bis[{O,O-dimethyldithiophosphato}oxomolybdenum(V) was prepared by dropwise addition of an ethanolic solution of the ammonium salt of O,O-dimethyldithio-phosphoric acid to a hot aqueous solution of MoCl₅. The X-ray structure of Mo₂O₂(Φ-S₂)[S₂P(OMe)₂]₂.C₆H₆ was determined. Crystal data: Monoclinic, P2₁/n, a = 6.9788(6), b = 22.616(3), c = 14.633(1) Å, β = 101.193(9)°, V = 2265.5(4) Å⁻³, Z = 4. The immediate environment around the two molybdenum atoms is essentially square pyramidal if the Mo—Mo interaction is ignored. The terminal oxygen atoms are in the syn conformation.     

Synthesis, crystal structures, and properties of two manganese(II)-nitroprusside complexes

Two new manganese(II)-1,10-phenanthroline-nitroprusside complexes, [Mn(phen)₃][Fe (CN)₅(NO)]⋯2H₂O⋯0.25CH₃OH (1) and [Mn(phen)₂(H₂O)₂][Fe(CN)₅(NO)]⋯H₂O (2) (where phen is 1,10-phenanthroline) have been synthesized and characterized by X-ray diffraction, electronic paramagnetic resonance (E.P.R.) and IR analyses. Complex 1 crystallizes in the monoclinic space group P2₁/n, with lattice parameters a = 10.0441(15) Å, b = 19.668(2) Å, c = 19.938(3) Å,  β =100.427(14)°, V = 3873.7(10) ų, Z = 4; complex (2) crystallizes in the monoclinic space group C2/c, with a = 17.120(2) Å, b = 13.7925(19) Å, c = 14.4362(17) Å, β = 107.962(12)°, V = 3242.6(7) ų, Z = 4. In the two compounds, three phen ligands 1, or two phen ligands and two cis-related aqua molecules 2, are in a distorted octahedral arrangement around the Mn(II) ion. The nitroprusside anion, [Fe(CN)₅(NO)]²⁻, acts as a counterion. It is intriguing that in complex 2 no cyano bridges are present with two water molecules coordinated to the Mn(II) ion considering that usually the cyano nitrogen atoms are strong donors and could readily replace the coordinating solvent water molecules. Abundant hydrogen bond interactions and π–π stacking between the phen rings in two complexes lead to three-dimensional supramolecular networks.     

Synthesis and Crystal Structure of 1,3-Bis[2-(pyrrol-2-carbonyloxy)ethoxy]Benzene

Abstract  

A new compound, 1,3-bis[2-(pyrrol-2-carbonyloxy)ethoxy]benzene (1), was synthesized and characterized by X-ray diffraction. The crystal is monoclinic, space group P2₁/c with a = 6.3571(7), b = 11.0416(11), c = 28.156(3) ?, b = 92.821(2), V = 1974.0(4) ?³, Z = 4, Dc = 1.293 g/cm³, F(000) = 808, μ = 0.097 mm⁻¹. The final R = 0.0395 and wR = 0.0927 for 3478 observed reflections with I > 2 σ(I), and R = 0.0660 and wR = 0.1058 for all reflections. The title compound assembles into 2-D structure through a catemer type N–H⋯O hydrogen bonding motif and further forms 3-D structure through C–H···O hydrogen bonds.     

Synthesis and structural characterization of the dinuclear bis(glutarato)bis(urea)copper(II)complex, dihydrate

The complex [Cu(OOC-(CH₂)₃-COO)(O=C(NH₂)₂]₂·2H₂O has been synthesized and characterized by X-ray crystallography. It crystallizes in the triclinic system P-1 with a = 8.003(2) ?, b = 8.611(2) ?, c = 8.620(2) ?, α = 96.14(3)°, β = 116.66(2)°, γ = 105.66(4)° and V = 492.9(3) ?³. The structure consists of discrete centrosymmetric binuclear units and water molecules. The Cu(II) ions adopt a square-pyramidal coordination with four oxygen atoms of four bridging carboxylate and one carbonyl oxygen of the monodentate urea ligand. There is a very strong interaction between the two copper centers in binuclear entities (CuCu: 2.6266(15) ?).     

Synthesis and Characterization of the Osmium Compound <Emphasis Type="Italic">cis</Emphasis>(CO)<Emphasis Type="Italic">–</Emphasis>ClOs(CO)<Subscript>2</Subscript>(bpcd)[C(O)Et]

Photochemical activation of the triosmium cluster Os₃(CO)₁₂ in CH₂Cl₂ solvent and ethylene, followed by treatment with the diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd), furnishes the new octahedral compound cis(CO)–ClOs(CO)₂(bpcd)[C(O)Et] in low yield. The title compound has been isolated and characterized in solution by IR and ¹H NMR spectroscopies, with the solid-state structure of cis(CO)–ClOs(CO)₂(bpcd)[C(O)Et] determined by X-ray diffraction analysis. cis(CO)–ClOs(CO)₂(bpcd)[C(O)Et] crystallizes in the triclinic space group P-1, a = 10.043(2), b = 11.455(2), c = 16.221(3) Å, α = 74.900(3)°, β = 76.150(3)°, γ = 76.221(2)°, V = 1718.2(5) ų, Z = 2, D _cacl = 1.717 Mg/m³; R = 0.0453, R _w = 0.0778 for 6703 observed reflections with I > 2σ(I). The presence of the chlorine and propanioyl groups in cis(CO)–ClOs(CO)₂(bpcd)[C(O)Et] is structurally confirmed, and the origin of the these groups from the reaction solvent and ethylene is discussed.     

A microporous coordination polymer with 1-D channels constructed from a basic reaction system

A ytterbium coordination polymer, {[Yb₂(OH)₂(atpt)₂]·0.5H₂O} _n , (atpt = 2-aminoterephthalate) was synthesized by using the reaction of YbCl₃·6H₂O with 2-aminoterephthalic acid under hydrothermal condition and structurally characterized by single-crystal X-ray diffraction method. The Yb(III) complex crystallizes in the monoclinic system P2/c with a = 13.1306(9) ?, b = 7.8049(5) ?, c = 21.5601(12) ?, β = 111.481(3)°, V = 2056.1(2) ?³, Z = 4. There are two crystallographically independent Yb³⁺ ions in the crystal, in which one is seven-coordinate, the other is eight-coordinate, and both of them are in oxygen environments. The ligand atpt adopts two coordination modes, bis(bridging bidentate) and bis(chelating and bridging tridentate). In addition, every hydroxyl group adopts μ₃-O mode linking three Yb³⁺ ions. It is through the linkage of atpt and hydroxyl group that ytterbium ions are linked together to form a 3-D structure with an open metal–organic framework.     

Structural characterization of the edge double-bridged triruthenium cluster complex Ru3(μ-Cl)2(CO)8(PPh3)2

The title compound is Ru₃(-Cl)₂(CO)₈(PPh₃)2. Crystal data: formula C₄₄H₃₀O₈Cl2P2Ru₃;f _w =1122.9; monoclinic,P2₁; cell parameters (at 293 K)a=10.971(2) Å,b=17.066(2) Å,c=11.833(2) Å,=92.91(1)°,V=2213 ų,Z=2, _calcd=1.68, _meas=1.68. Final discrepancy indices areR(F)=0.030,R _W (F)=0.036. The structure consists of an open trinuclear unit involving two metal-metal bonds [Ru(1)-Ru(2)=2.845(1) Å, Ru(2)-Ru(3)=2.860(1) Å]. The open edge of the metal framework [Ru(1)Ru(3)=3.254(1) Å] is supported by two symmetric bridging chloride ligands [Cl(1)-Ru(1)=2.461(2) Å; Cl(1)-Ru(3)=2.464(2) Å; Cl(2)-Ru(1)=2.470(2) Å; Cl(2)-Ru(3)=2.472(2) Å]. Both phosphorus ligands are cis to the Cl atoms and trans to the unique ruthenium atom Ru(2). Geometric features of the edge dibridged complex are discussed.     

Crystal structure analyses of bis(triphenyl- phosphoranyliden)ammonium bis(pentafluoroethyl) argentate, [Ph3P=N=PPh3][Ag(C2F5)2] and bis[bis(triphenylphosphoranyliden)ammonium] tetrachloro-diargentate, [Ph3P=N=PPh3]2[ClAg(μ-Cl)2AgCl]

Bis(triphenylphosphoranyliden)ammonium bis(pentafluoroethyl)argentate, [Ph₃P=N= PPh₃][Ag(C₂F₅)₂] (1) and bis[bis(triphenylphosphoranyliden)ammonium]tetrachloro-diargentate, [Ph₃P=N=PPh₃]₂[ClAg(μ-Cl)₂AgCl] (2) were crystallized from the reaction mixture of pentafluoroethylsilver(I) and bis(triphenylphosphoranyliden)ammonium chlo-ride. Crystallization of 1 occurs in the centrosymmetric monoclinic space group P2₁/c (No. 14) with a = 17.083(2) Å, b = 11.600(2) Å, c = 19.833(2) Å, β = 109.66(1)°, V = 3700.8(7) ų, Z = 4. 2 crystallizes in the centrosymmetric orthorhombic space group Pbca (No. 61) with a = 19.540(1) Å, b = 15.926(1) Å, c = 20.160(1) Å, V = 6273.6(3) ų, Z = 8.