Synthesis and Crystal Structure of [CpRu（η^5-C5H5）（dppc）Cl][PF6]

1INTRODUCTION The fragment[Ru(η5-C5H5)(PPh3)2Cl]plays an important role in the organo-ruthenium chemistry development,and has been used as a versatile star-ting material for other compounds due to its stability and facile manipulation.Much work has shown that a wide range of ligands with different steric and electronic properties can displace not only the Cl ligand but also the phosphine groups in[Ru(η5-C5H5)(PPh3)2Cl][1].The interest in this fragment and related derivatives concer…     

Synthesis and Crystal Structure of [Cp＊Ru（η^6-C6H5BPh3）]

1 INTRODUCTION The use of organometallic building blocks in the crystalline materials engineering allows us to intro- duce the characteristics of transition metals, such as variable oxidation, spin states and ionic charges, which is of great significance for the preparation of novel materials. In recent years, some complexes with structure of [Cp*M(η6-C6H5)] group and related complexes as building blocks have already been synthesized[1～3]. One example was prepared by the reaction of [C…     

Organometallic polymorphism. Synthesis and structural characterization of two forms of [Ru(η6-C6H6)(η6-C6H4(CH3)COOCH3)][BF4]2 and the phase transition in [Ru(η5-C5H5)(η6-C6H5OH)][PF6]

The synthesis and structural characterization of the complex [Ru(η⁶-C₆H₆)(η⁶-C₆H₄(CH₃)COOCH₃)] [BF₄]₂ (2) and of its precursor [Ru(η⁶-C₆H₄(CH₃)COOCH₃)Cl₂]₂ (1) are reported. Compound (2) has been characterized in two polymorphic modifications (2a and 2b) and the molecular organization in the solid state has been investigated. The complex [Ru(η⁵-C₅H₅)(η⁶-C₆H₅OH)][PF₆] (3) has also been investigated; it has been shown to possess a disorder similar to that observed in the high temperature phase of related systems such as [Ru(η⁵-C₅H₅)(η⁶-C₆H₆)][PF₆].     

Continuous photochemical generation of catalytically active [CpRu]+ complexes from CpRu(η6-C6H6)PF6

Inter- and intramolecular ene-yne coupling reactions catalyzed by a species generated in situ via photolysis of CpRu(η(6)-C(6)H(6))PF(6)--an inexpensive, readily available, and shelf-stable complex--have been demonstrated under conditions of continuous flow. Importantly, the catalyst can be recovered quantitatively at the end of the reaction. Various functional groups are tolerated by the reaction, which affords skipped diene products in high yields.     

The synthesis of new paracyclophane complexes of ruthenium(II): Crystal structure of [Ru(η6-C16H16)Cl(C5H5N)2][PF6]

The dimer [Ru(η⁶-C₁₆H₁₆)Cl₂]₂ reacts with ligands L (L  PMe₂Ph, PPh₃, C₅H₅N) to give both neutral monomeric [Ru(η⁶-C₁₆H₁₆)Cl₂L] and cationic monomeric [Ru(η⁶-C₁₆H₁₆)ClL₂]⁺ products. One example, [Ru(η⁶-C₁₆H₁₆)Cl(C₅H₅N)₂]-[PF₆], has been characterised by X-ray crystallography. Reaction with the bidentate ligand 2,2′-bipyridyl gives the mononuclear cation [Ru(η⁶-C₁₆H₁₆)Cl(bipy)]⁺, isolated as its [BPh₄]⁻ salt, whereas reaction with OMe⁻ or OEt⁻ gives dinuclear products [Ru(η⁶-C₁₆H₁₆)₂(OR)₃]⁺.     

Synthesis and Crystal Structure of [Ca（DMF）6][Mo6Br8Cl6]

1INTRODUCTION Molybdenum(II)halide clusters containing[Mo6-X8]4 cores have been the subject of interest for over five decades[1].This octahedral cluster-type comple-xes comprise an important,and in a sense archetypal,class of higher nuclearity transition metal cluster com-plexes.Their high symmetry,photochemical and pho-tophysical properties as well as structural relation-ships to cluster complexes of other elements exhibit significant interest[2].In addition,there is a structural simila…     

Triethylaluminum-Based Ferrocenylalanes. Synthesis and Crystal Structure of (η5−C5H5)Fe[η5−C5H4Al2(C2H5)4Cl]

Abstract

The trietheylaluminum based ferrocenylalane (η⁵?C₅H₅)Fe[η⁵?C₅H₄Al₂(C₂H₅)₄Cl] was prepared from the reaction of triethylaluminum with chloromercuriferrocene in toluene and characterized by single crystal X-ray diffraction. The compound crystallizes in the triclinic space group P 1 with unit cell dimensions a = 9.353(3) Å, b = 10.281(7) Å, c = 11.599(9) Å, α = 79.64(7)°, β = 69.41(6)°, γ = 84.33(4)°, and Z = 2 for D_c = 1.27 g cm^?3. Full-matrix least-squares refinement has led to a final R factor of 0.068 based on 1866 independent observed reflections. The two diethylaluminum units are bridged by a chlorine atom and one carbon atom of a cyclopentadienyl group, thus forming an Al-Cl-Al-C ring. The four-membered ring is planar to within 0.02 Å. The Al-Cl distances are 2.404(4) Å and 2.266(5) Å. The Al-Cl-Al angle is 78.9(1)° while the Al-C-Al angle is 91.3(4)°. No significant aluminum-iron interaction is observed (Al… Fe = 3.137(4) Å).     

Crystal structure and thermal properties of [Pt(NH3)5Cl][ReCl6]Cl·H2O

The crystal structure of double complex salt [Pt(NH₃)₅Cl][ReCl₆]Cl·H₂O is determined. Crystallographic characteristics are: a = 23.9502(4) Å, b = 7.5963(1) Å, c = 8.9016(2) Å, V = 1619.49(5) ų, space group Pnma, Z = 4, d _x = 3.150 g/cm³. The packing of structural fragments is studied. It is shown that on heating the salt in a helium atmosphere up to 840 °C a mixture of two solid solutions of fcc Pt_0.90Re_0.10 and hcp Pt_0.25Re_0.75 forms.     

Synthesis and Crystal Structure of [ Cp* Ru(η6- C6H5B Ph3)]

The title complex [Cp*Ru(η6-C6H5BPh3)] has been synthesized by the reaction of [Cp*Ru(H2O)(NBD)]BF4 with H2 and NaBPh4, and its crystal structure was determined by singlecrystal X-ray diffraction analysis. It crystallizes in triclinic, space group P(1) with a = 11.0610(10), b = 11.2317(10), c = 12.3633(11) (A), α = 81.419(2), β = 67.8370(10), γ = 88.370(2)°, V= 1405.9(2) (A)3,Z= 2, C34H35BRu, Mr= 555.50, Dc = 1.312 g/cm3, F(000) = 576 and μ(MoKa) = 0.577 mm-1. The final R and wR are 0.0559 and 0.1483, respectively for 4365 observed reflections with I ＞ 2σ(Ⅰ). In the title complex, the four phenyl rings bonded to the B atom are deposited in a tetrahedral geometry,and one of the phenyl rings is η6-bonded to ruthenium.     

Molecular structure of two dicyclopentadienylmolybdenum derivatives containing a four-membered ring [Mo(η5-C5H5)2(2-NHNC5H4)][PF6] and [Mo(η5C5H5)2(2-ONC5H4)][PF6]

The structure of the new compound [Mo(η⁵-C₅H₅)₂(2-NHNC₅H₄)][PF₆] (1) has been determined. The crystals are orthorhombic, space group Pca2₁ with a 20.807(1), b 8.0030(8), c 10.056(3) Å, V 1674.5 ų, Z = 4. The structure of [Mo(η⁵-C₅H₅)₂(2-ONC₅H₄)][PF₆] (2) has also been determined. The crystals are orthorhombic, space group Pnma with a 12.727(3), b 10.174(2), c 12.918(1) Å, V 1672.8 ų, Z = 4. The structures were solved by Patterson and difference electron density syntheses and refined by least-squares to R of 0.028 for 1287 reflections for 1 and 0.059 for 1178 reflections for 2.Although not isostructural the two cationic complexes have equivalent geometries with the normal bent bismetallocene structure. For 1 the MoN bond lengths are 2.160(8) and 2.142(9) Å, with a NMoN bond angle of 59.8(3)°, whereas for 2 MoO is 2.142(10), MoN is 2.138(11) Å, the NMoO angle is 61.2(4)°. These parameters are discussed and compared with the corresponding data for similar biscyclopentadienyl complexes of molybdenum(IV). Extended Hückel molecular orbital calculations have been carried out to throw light on the nature of the bonding between the metal and the bidentate ligand.     

Synthesis and Crystal Structure of [Ni(Ⅱ)(L)(py)3]·(py)

The title complex, C37H34N6NiO5, has been prepared and characterized by X-ray diffraction analysis. It crystallizes in the monoclinic system, space group P21/c with a = 1.15244(8), b = 1.69679(12), c = 1.78341(13) nm, β = 102.2320(10)°, V = 3.4082(4) nm3, Z = 4, Mr = 701.41, F(000) = 1464, Dc = 1.367 g/cm3 and μ(MoKα) = 0.622 mm-1. The structure was refined to R = 0.0459 and wR = 0.1199 for 5718 observed reflections. The intramolecular hydrogen bonds in the crystal structure play important roles in the title complex's thermostability.     

Electron transfer in organometallic clusters: XIV. Crystal and electronic structures of the tricobalt carbon cluster (η5-C5H5)Fe[η5-C5H4-CCo3(CO)9] and the biscarbyne cluster (η5-C5H5)Fe[η5-C5H4CCo3(η5-C5H5)3CH]

The crystal and molecular structures of (η⁵-C₅H₅)Fe[η⁵--C₅H₄CCo₃(CO)₉] (1), Pna2₁, α 17.354, b 11.463, c 11.207 Å Z = 4, R = 0.053, R_w = 0.056 for 939 reflections (I>3σ(I)) at 293 K, and (η⁵-C₅H₅Fe[η⁵--C₅H₄CCo₃(η⁵C₅H₅)₃CH] (2), P2₁/n, a 13.807(9), b 11.254(4), c 13.991(9) Å, β 99.98(5)°, Z = 4, R = 0.033 and R_w = 0.033 for 3051 observed reflections (I>3σ(I)) at 180 K, have been determined by X-ray methods.The results provide a detailed characterisation of related tricobalt-carbon complexes directly bound to ferrocene residues. In 1 the ferrocenyl moiety tops the pyramidal CCo₃ cluster core, while in 2 the CCo₃C core is bipyramidal with a ferrocenyl substituent on one capping carbon atom and a hydrogen atom at the other. In both cases the ferrocenyl group is tilted towards one cobalt atom of the cluster core, a distortion believed to be the consequence of the non-degeneracy of the carbyne p(π) orbitals resulting from a cooperative π-interaction between the clusters and the ferrocenyl substituents.     

Synthesis and Crystal Structure of [Ni(II)(L)(py)_3]·(py)

1 INTRODUCTION Schiff bases and their metal complexes are useful reagents in organic synthesis[1], and they have exhi- bited some biological activities as anticancer and antitumor drugs[2]. The crystal structures and physi- cal and chemical properties of many Schiff bases and their transition metals complexes have been re- ported[3~5]. Further interest in the coordination che- mistry of nickel(II) arises from the role of these complexes in several catalytic reactions, such as electrocat…     

Synthesis, Characterization and Crystal Structure of [Co2Mo2(μ4-C2HPh)(μ-CO)4(CO)4(η5-C5H4C(O)Me)2]

The reaction of μ-alkyne-bridged dimolybdenum compound [Mo2(μ-C2HPh)(CO)4(η5-C5H4C(O)Me)2] 1 with Co2(CO)8 in refluxing toluene gave a new butterfly compound [Co2Mo2(μ4-C2HPh)(μ-CO)4(CO)4(η5-C5H4C(O)Me)2] 2 which was fully characterized by elemental analysis, IR, 1H NMR and X-ray single crystal diffraction techniques. 2 crystallized in monoclinic system, C30H20Co2Mo2O10, Mr=850.23, space group P21/a(#14), a=14.165(5), b=12.498(2), c=16.204(2)(A), β = 96.50(2)°, V = 2850(1)(A)3, Z = 4, Dc = 1.981 g cm-3, F(000)=1672, μ(MoKα)=20.41 cm-1, final R=0.030, Rw=0.039 for 4831 observable reflections with I>2σ(I). The structure contains a Co2Mo2 butterfly core, and each Mo-Co bond is spanned by an asymmetric semi-bridging carbonyl ligand.     

Selective dilithiation of [Ti(η(5)-C5H5)(η(8)-C8H8)] and subsequent conversion into neutral and cationic ansa-complexes

Selective dimetalation of a sandwich complex featuring the cyclooctatetraene ligand has been accomplished for the first time. The isolation of the dilithiated species 1 subsequently enabled the isolation of a paramagnetic [2]stannatitanoarenophane (2) via salt elimination reaction. Chemical oxidation resulted in the formation of a rare example of a cationic ansa-complex (3).     

Regioselective permethylation,perallylation and perbenzylation of the arene ligand in [Ru(η5-C5Me5)(η6-C6Me6)][PF6]: a remarkable periodic effect

The reactions of [MCp^*(η⁶-C₆Me₆)][PF₆], M = Fe: 1, Ru: 2, Cp^* = η⁵-C₅Me₅, with KOH (in DME) or tert-BuOK (in THF) and methyl iodide, allyl bromide or benzyl bromide are regioselective on the arene ligand only for 2, giving the complexes [RuCp^*{η⁶-C₆(CH₂R)₆}][PF₆], R = methyl (3), allyl (4) or benzyl (5), although some formations of C-C bonds also occur on the Cp^* ligand in the case of the reactions of allyl and benzyl bromides. This contrasts with the complete lack of regioselectivity formerly observed with the iron analogue 1, and is best taken into account by the difference of steric effects which are less marked in 2 than in 1.     

Synthesis and Crystal Structure of [EDA][Ni（dmit）2]3

The crystal structure of the compound [EDA][Ni(dmit)2]3 (EDA=2-diethylamino-1,3-dithioanylium; dmit=1,3-dithiole-2-thione-4,5-dithiolate)C25H14NNi3S32, has been determined by single crystal X-ray diffraction at 300K. The crystal is triclinic with space group P, a=11.252, b=12.192(2), c=20.055(6) , α=108.127(2), β=106.287(8), γ=90.005(9)°; V=2498.3(3) 3, Z=2, Mr=1530.38, Dc=2.03(2) g/cm3. Final R and Rw values were 0.0603 and 0.0704, respectively. The structure consists of thick layers of stacked Ni(dmit)2 entities separated by EDA cations. This salt shows semiconducting behaviour with room temperature conductivity of 0.2 Scm-1 and activation energy of 0.11 eV.     

The X-ray crystal structure of di-η5-cyclopentadienylthiophenolatoamminemolybdenum(IV) hexafluorophosphate solvate [Mo(η5-C5H5)2(NH3)(SC6H5)][PF6] · (CH32CO

Crystals of [Mo(η⁵-C₅H₅)₂(NH₃)(SC₆H₅)][PF₆] · (CH₃)₂CO solvate are monoclinic, space group P2₁/n, a 9.777(1), b 11.6343(2), c 19.656(4) Å, β 93.60(1)°, V 2231-46 ų, Z  D_c 1.617 g cm⁻³, μ(Mo-K_α) 7.21 cm⁻¹. The structure was solved by Patterson and difference Fourier electron density synthesis and refined to R (F)  0.047 and R_w(F)  0.057 for 3293 observed reflections. The molybdenum atom has the usual distorted tetrahedral geometry comprising the two MoCp (Cp  η⁵-C₅H₅) ring normals (MoCp 1.988(13), 1.989(15) Å), one Mo-NH₃ (MoN 2.226(12) Å), and one MoSc₆H₅ (MoS 2.465(5) Å). Extended HMO and steric energy calculations were made in order to account for the geometry adopted by the thiolato ligand in this complex.     

Replacement of terminal and bridging oxo groups by phenylimido groups in (η-C5H5)OMo(μ-O)2OMo(η-C5H5) giving (η-C5H5)(NPh)Mo(μ-NPh)2Mo(NPh)(η-C5H5)

The treatment of (η-C₅H₅)OMo(μ-O)₂MoO(η-C₅H₅) with excess phenylisocyanate at reflux in tetrahydrofuran yields the arylimido-substituted complex (η-C₅H₅)(NPh)Mo(η-NPh)₂Mo(NPh)(η-C₅H₅), which has been characterized by elemental analysis, and mass, IR and ¹H NMR spectra.