Cationic rhodium tetrafluorobenzobarrelene complexes with diolefin or arene ligands,crystal structures of [Rh(TFB)(arene)] ClO4, (arene = C6Me6, C6H3Me3, C6H4Me2)

The preparation and properties of complexes of the general formulae [Rh(TFB)(diolefin)]ClO₄, [Rh(TFB)(arene)]ClO₄ and [Rh(TFB)L₂]ClO₄, (TFB = tetrafluorobenzobarrelene, L = dimethylsulfoxide and tetrahydrothiophen) are described. The crystal structures of the arene complexes (arene = C₆Me₆, C₆H₃Me₃ and C₆H₄Me₂) have been solved by X-ray methods. The three compounds crystallize in quite similar lattices: R3c, a = b = 27.122, 26.233, 25.731 and c = 17.079, 16.388, 16.256 Å, respectively. δR-plots for about 2000 reflections show the agreement in the refinements carried out up to R-values of 5%, 5% and 4% respectively. The Rh atom is coordinated to the double bonds of the TFB and to the arene ring in all three compounds, but the deviation from planarity of the arene and its relative position with respect to the TFB moiety varies.     

Synthesis, molecular, crystal and electronic structure of [(C6H6)RuCl(1,10-C12H8N2)]Cl

The [(C₆H₆)RuCl(1,10-C₁₂H₈N₂)]Cl complex has been prepared and studied by IR, UV-Vis, ¹H NMR spectroscopy and X-ray crystallography. The complex was prepared in reaction of [(C₆H₆)RuCl₂]₂ with 1,10-phenatroline in acetone. The electronic spectrum of the compound has been calculated using the TDDFT method.     

Crystal structures of [Rh(η-C5H5)(C3S5)] and [Rh(η-C5Me5)(C3S5)]2 and properties of their oxidized species

[Rh(η⁵-C₅H₅)(C₃S₅)] and [Rh(η⁵-C₅Me₅)(C₃S₅)]₂ [C₃S₅²⁻=4,5-disulfanyl-1,3-dithiole-2-thionate(2-)] were prepared by reactions of [NMe₄]₂[C₃S₅] with [Rh(η⁵-C₅H₅)Cl₂]₂ and [Rh(η⁵-C₅Me₅)Cl₂]₂, respectively. Their X-ray crystal structural analyses revealed a monomeric form for the former complex and a dimeric geometry containing bridging S-Rh-S bonds for the latter in the solid state. They were reacted with bromine to afford [RhBr(L)(C₃S₅)] (L=η⁵-C₅H₅ and η⁵-C₅Me₅) with the Rh-Br bond and one electron-oxidation on the C₃S₅ ligand. ESR spectra and spin densities for these oxidized species are discussed.     

Synthesis, structure and optical properties of new organic-inorganic haloplumbates complexes (C5H10N3)PbX4 (X=Br, Cl), (C2H2N4)PbBr3

Layered organic-inorganic composite materials (C₅H₁₀N₃)PbX₄ (X=Br 1, Cl 2) containing histaminium dications were grown via a solution-cooling process, and their structure and optical properties were determined. The organic ligand-histaminium introduced into the corner-sharing octahedra of the ‘PbX₄-layer’ contains both primary ammonium and imidazolium different from the traditionally primary amine found in this system. As comparison, another analogous amine of 3-amino-1,2,4-triazol was used as ligand to coordinate with PbBr₂ in acid solution. A novel complex (C₂H₂N₄)PbBr₃ (3) was obtained with zigzag PbBr₂ chains different from the PbX₄ layer in compound as 1 and 2. The hybrid (C₅H₁₀N₃)PbX₄ show exciton absorption at 339 nm for X=Cl and 419 nm for X=Br with the corresponding emission at 360 and 436 nm, respectively. The different PbBr₂ chain structure of compound 3 does not show photoluminescence.     

三元配合物Tm[(C5/sub>H8NS2)3(C12H8N2)]的热化学性质研究

在无水乙醇中，用吡咯烷二硫代氨基甲酸铵(APDTC)和1,10-邻菲咯啉(o-phen·H₂O)与TmCl₃·3.65H₂O作用，合成了未见文献报道的三元固态配合物，确定它的组成为Tm[(C_{5/sub>H8NS2)3(C12H8N2)]。 用RD496-Ⅲ微量热计测定了298.15 K下水合氯化铥及两个配体在无水乙醇中的溶解焓，两个配体醇溶液的混合焓及不同温度下标题化合物液相生成反应的焓变。在实验和计算基础上，得到了液相生成反应的热力学参数(活化焓、活化熵和活化自由能)，速率常数和动力学参数(表现活化能、频率因子和反应级数)。通过合理的热化学循环，求得了298.15 K时标题化合物的固相生成反应焓变；推导了用该热量计测定固态物质比热容的计算式，并测定了题目配合物298.15 K的比热容。用RBC-Ⅱ精密转动弹热量计测定了题目配合物的恒容燃烧热， 计算了它们的标准摩尔燃烧焓和标准摩尔生成焓。}     

The crystal and molecular structure of dicarbonylbis(diphenylethylphosphine) platinum(0) Pt(CO)2[P(C6H5)2(C2H5)]2

The complex dicarbonylbis(diphenylethylphosphine)platinum, Pt(CO)₂[P(C₆H₅)₂(C₂H₅)]₂, crystallizes in either of the enantiomorphous space groups P3₁21 (No. 152) and P3₂21 (No. 154) with cell dimensions a = 10.64(1), c = 22.06(1) Å, U = 2163 ų; p_c = 1.564 g/cm³ for Z = 3, p_m = 1.55(3) g/cm³. The intensities of 1177 independent reflections have been determined by counter methods with MoKα monochromatized radiation. The structure has been solved by the heavy atom method. The refinement, carried out by full-matrix least squares down to a final R factor of 0.042, has enabled the absolute configuration of the crystal sample (space group P3₁21) to be ascertained. The molecule is roughly tetrahedral, and has the metal atom lying on a two-fold axis of the cell. Bond parameters are: PtC = 1.92(2) Å, PtP = 2.360(4) Å, CPtC = 117(1)° and PPtP = 97.9(2)°. The PtC₂ and PtP₂ moieties make a dihedral angle of 86.0(3)°. The overall C₂ symmetry of the molecule is probably only a statistically averaged situation, a disorder in the PtCO interactions being apparent from the orientations of the thermal ellipsoids of the C and O atoms.     

Synthesis, crystal structure and NLO property of a nonmetal pentaborate [C6H13N2][B5O6(OH)4]

A nonmetal pentaborate [C₆H₁₃N₂][B₅O₆(OH)₄] (1) has been synthesized by 1,4-diazabicyclo[2.2.2] octane (DABCO) and boric acid, and characterized by single-crystal X-ray diffraction, FTIR, elemental analysis, and thermogravimetric analysis. Compound 1 crystallizes in the monoclinic system with space group Cc (no. 9), a=10.205(2) Å, b=14.143(3) Å, c=11.003(2) Å, β=113.97(3)°, V=1451.1(5) Å³, Z=4. The anionic units, [B₅O₆(OH)₄]⁻, are interlinked via hydrogen bonding to form a three-dimensional (3D) supramolecular network containing large channels, in which the protonated [C₆H₁₃N₂]⁺ cations are located. Second-harmonic generation (SHG) measurements on the powder samples reveal that 1 exhibits SHG efficiency approximately 0.9 times that of potassium dihydrogen phosphate (KDP).     

Cl+C2H6→HCl+C2H5反应的准经典轨线研究

用三原子模型的准经典轨线方法研究了Ｃｌ与Ｃ２Ｈ６（ｖ＝０，ｊ）的反应。计算结果表明，反应产物ＨＣｌ的角度分布基本上为各向同性，其振动分布处于基态，与实验结果相一致。对反应轨线的研究表明，该反应为一直接反应，而且反应碰撞在低及高的碰撞参数下的机理不一样，在低碰撞参数下反应碰撞是直接完成的，产物ＨＣｌ以向后散射为主，转动基本上是冷的，但比高碰撞参数下的热。在高的碰撞参数下则生成短寿命的碰撞复合物，产物     

Hydrothermal synthesis of [C6H16N2][In2Se3(Se2)]: A new one-dimensional indium selenide

A new organically templated indium selenide, [C₆H₁₆N₂][In₂Se₃(Se₂)], has been prepared hydrothermally from the reaction of indium, selenium and trans-1,4-diaminocyclohexane in water at 170 °C. This material was characterised by single-crystal and powder X-ray diffraction, thermogravimetric analysis, UV-vis diffuse reflectance spectroscopy, FT-IR and elemental analysis. The compound crystallises in the monoclinic space group C2/c (a=12.0221(16) Å, b=11.2498(15) Å, c=12.8470(17) Å, β=110.514(6)°). The crystal structure of [C₆H₁₆N₂][In₂Se₃(Se₂)] contains anionic chains of stoichiometry [In₂Se₃(Se₂)]²⁻, which are aligned parallel to the [1 0 1] direction, and separated by diprotonated trans-1,4-diaminocyclohexane cations. The [In₂Se₃(Se₂)]²⁻ chains, which consist of alternating four-membered [In₂Se₂] and five-membered [In₂Se₃] rings, contain perselenide (Se₂)²⁻ units. UV-vis diffuse reflectance spectroscopy indicates that [C₆H₁₆N₂][In₂Se₃(Se₂)] has a band gap of 2.23(1) eV.     

Dreikern- sowie homo- und heterometall-zweikernkomplexe mit der baueinheit C5Me5Rh. Die kristallstruktur von C5Me5[P(OMe)3[Rh(μ-CO)2RhC5Me5

C₅Me₅Rh(L)P₂Me₄ (L = CO, C₂H₄) reacts with [C₅Me₅Rh(μ-CO)]₂, to give the trinuclear complexes C₅Me₅(L)Rh(μ-P₂Me₄)RhC₅Me₅(μ-CO)₂RhC₅Me₅ (VI, VII). In the reactions of C₅Me₅Rh(CO)P₂Me₄ with C₅H₅(CO)₂ (M = Rh, Co) and C₅H₄RMn(CO)₃ (R = H, Me), the homo- and hetero-metallic binuclear compounds C₅Me₅(CO)Rh(μ-P₂Me₄)M(CO)C₅H₅ (VIII, IX) and C₅Me₅(CO)Rh(μ-P₂Me₄)Mn(CO)₂C₅H₄R (X, XI) are obtained in almost quantitative yield. The X-ray structure of the complex C₅Me₅[P(OMe)₃]Rh(μ-CO)₂RhC₅Me₅ (III), which is structurally related to VI and VII, has been determined. The molecule contains an unsymmetrical, non-planar Rh₂C₂-skeleton with different Rh-C(O) bond lengths. The Rh-Rh distance is 268.5(1) pm; the planes of the two five-membered rings form an angle of 62.6°.     

Arene-rhodium(I) complexes with trimethyltetrafluorobenzobarrelene. Crystal structure of [Rh(Me3TFB)(1,4-C6H4Me2)]ClO4

The preparation of arene-rhodium(I) complexes of the general formula Rh(Me₃TFB)PhBPh₃ and [Rh(Me₃TFB)(arene)]ClO₄ (Me₃TFB = trimethyltetrafluorobenzobarrelene; arene = C₆H_6?nMe_n (n = 0, 1, 2, 3, 4 or 6); C₆H_6?nX_n (X = F, n = 2 or 6; X = Cl, n = 1 or 2) are described. For arenes of the type C₆H_6?nX_n the dissociation of the coordinated arene (studied by NMR spectroscopy in deuteroacetone) is complete, but for arenes of the type C₆H_6?nMe_n it decreases with increasing methyl substitution in the arene ligand.The crystal structure of [Rh(Me₃TFB)(1,4-C₆H₄Me₂)]ClO₄ has been determined by X-ray diffraction. The compound crystallizes in the Pbca space group, with lattice periodicities of 17.7393(4), 15.7816(3) and 16.0071(3) Å. δR-analysis, for the 3953 total recorded reflections, support the refinement carried out to a final R-value of 0.062. The bonding of the arene to the rhodium is η⁶, with the ring slightly puckered to give a distorted skew conformation.     

Arene-iridium(I) complexes. Crystal structure of [Ir(Me3TFB)(C6Me6)]ClO4

The crystal structure of [Ir(Me₃TFB)(C₆Me₆)]ClO₄ has been determined by X-ray diffraction. Lattice constants are a 16.9092(7), b 17.7120(7), c 16.8635(6) Å and β 97.984(3)° in a C2/c monoclinic lattice. The agreement factors are R, 0.038 and R_w 0.048 for the 3321 reflexions with I > 3σ(I). The coordination characteristics are similar to those of the corresponding rhodium analogues.     

Crystal and molecular structure of [{Rh(C5Me5)}3Cl5np3]PF6 · 0.5 C3H8O

The crystal and molecular structure of the monoligand trimetallic complex [{Rh(C₅Me₅)}₃Cl₅np₃]PF₆ · 0.5 C₃H₈O (np₃  tris(2-diphenylphosphinoethyl)-amine) have been established by a single-crystal X-ray diffraction study. The cation of the complex contains two Rh(C₅Me₅)Cl₂ units each bound through the metal to one phosphorus atom of the ligand and a Rh(C₅Me₅)Cl group in which the rhodium is bound to the third phosphorus atom and to the nitrogen of the tetradentate ligand.The crystals are triclinic, space group P$\text{1}$, with cell dimensions a 28.598(8), b 13.757(4), c 10.748(3) Å, α 90.69(4), β 96.67(4), γ 99.71(4)°, D_c 1.38 g cm^?3 for Z  2. The structure was solved by three dimensional Patterson and Fourier syntheses and refined by least-squares techniques to a final conventional R value of 0.098.     

Die thermische reaktion von C5H5(CO)2FeNa mit benzimidchloriden C6H5(Cl)CNR

η⁵-C₅H₅(CO)₂FeNa reacts with the benzimide chlorides C₆H₅(Cl)CNR (R  CH(CH₃)₂, C₆H₅) in boiling THF to give the η¹-iminoacyl complexes η⁵-C₅H₅ (CO)₂Fe[η¹-C(C₆H₅)NR]. Alternatively, the new Fe complexes [η⁵-C₅H₅(CO)Fe$\text{C(C}{}_6\text{H}{}_5\text{)N(CH}{}_3\text{)C(C}{}_6\text{H}{}_5\text{)N}$CH₃PF₆ (IV) and [η⁵-C₅H₅(CO)₂FeC(C₆H₅)N(CH₃)C(C₆H₅)NCH₃]PF₆ (V) are formed under the same conditions, if R  CH₃. Hudrolysis of the CN single bond of the ligand in V, not stabilized by a chelate effects as in IV, results in the formation of [η⁵-C₅H₅(CO)₂FeC(C₆H₅)NHCH₃]PF₆ (VII). Reaction of η⁵-C₅H₅(CO)₂ with N-benyzylbenzimido chloride yields η⁵-C₅H₅(CO)₂FeCH₂C₆H₅ as the only isolated product.     

Hydrogen-bonded systems between monocarboxylic acids and the trinuclear cluster cation [H3Ru3(C6H6)(C6Me6)2(O)]: cold-spray ionisation mass spectroscopic and X-ray crystallographic studies

The hydrogen-bonded systems formed between monocarboxylic acid derivatives and the trinuclear arene-ruthenium cluster cation [H₃Ru₃(C₆H₆)(C₆Me₆)₂(O)]⁺ (1) have been studied in solution by cold-spray ionisation mass spectroscopy (CSI-MS) and in the solid state by single-crystal X-ray structure analysis of the tetrafluoroborate salts. The presence of 1:1 (acid:cluster) adducts in acetone solution has been clearly demonstrated by CSI-MS. Single-crystal X-ray structure analyses of selected acid-cluster complexes show that in every case the hydroxyl of the acid function interacts strongly with the μ₃-oxo ligand of cation 1, the O ? O distance ranging from 2.499(9) to 2.595(11) Å.     

新型一维链状配位聚合物[Cd2(C23H14O6)2(C10H9N3)2(H2O)]n的研究

配位超分子聚合物的设计合成与应用研究一直是配位化学、超分子化学、生物无机化学及材料科学等领域的热点研究课题之一,具有微孔结构的配位聚合物吸引了许多科学家的目光,这不仅因为该类配合物具有新颖的结构,展现出多种诱人的拓扑结构,更主要的 是因为它们在离子交换、催化、磁性材料、光学材料及气体贮存领域的应用潜力[1～3].     

X-ray crystal structures and solution dynamics of sodium organofluorotitanates [Na{Ti2(C5Me5)2F7}] and [NaTi6(C5Me5)5F20(H2O)]·(THF)

[Na{Ti₂(C₅Me₅)₂F₇}] (1) was prepared from sodium fluoride and [{Ti(C₅Me₅)F₃}₂] [H.W. Roesky, et al., Angew. Chem. Int. Ed. Engl. 31 (1992) 864-866]. The solid-state 1 consists of a polymeric chain of two rows of dititanate anions [Ti₂(C₅Me₅)₂F₇]⁻ connected by sodium ions in the middle of the chain. Each sodium ion is coordinated by five fluorine atoms from three [Ti₂(C₅Me₅)₂F₇]⁻ anions. The variable-temperature ¹⁹F NMR of CD₃CN solution of 1 revealed interconversions of monomeric species [Na(CD₃CN)_n{Ti₂(C₅Me₅)₂F₇}] (1solv) with different number of CD₃CN ligands on the sodium ion. The addition of HMPA to the CD₃CN solution of 1 allows ¹⁹F NMR observation of 1·HMPA (1a) and 1·HMPA·CD₃CN (1b) in the slow exchange. The solid-state structure of [NaTi₆(C₅Me₅)₅F₂₀(H₂O)]·(THF) (2·THF) reveals the sodium ion coordinated by four fluorine atoms from the anion [Ti₂(C₅Me₅)₂F₇]⁻ and by three fluorine atoms from the cluster [Ti₄(C₅Me₅)₃F₁₃(H₂O)].     

An ab initio study of the Cl(P)+C2H6→C2H5+HCl abstraction reaction

Electronic energies, geometries, and harmonic vibration frequencies for the reactants, products, and transition state for the Cl(³P)+C₂H₆→C₂H₅+HCl abstraction reaction were evaluated at the HF and MP2 levels using several correlation consistent polarized-valence basis sets. Single-point calculations at PMP2, MP4, QCISD(T), and CCSD(T) levels were also carried out. The values of the forward activation energies obtained at the MP4/cc-pVTZ, QCISD(T)/cc-pVTZ, and CCSD(T)/cc-pVTZ levels using the MP2/cc-pVTZ structures are equal to −0.1, −0.4, and −0.3 kcal/mol, respectively. The experimental value is equal to 0.3±0.2 kcal/mol. We found that the MP2/aug-cc-pVTZ adiabatic vibration energy for the reaction (−2.4 kcal/mol) agrees well with the experimental value −(2.2–2.6) kcal/mol. Rate constants calculated with the zeroth-order interpolated variational transition state (IVTST-0) method are in good agreement with experiment. In general, the theoretical rate constants differ from experiment by, at most, a factor of 2.6.     

Kristall- und molekülstruktur von hexaphenyldistannylselenid (C6H5)3SnSeSn(C6H5)3

The crystal and molecular structure of hexaphenylditin selenide (C₆H₅)₃SnSeSn(G₆H₅)₃ was determined by X-ray diffraction data and was refined to R  0.055. The compound is monoclinic, space group P2₁, with a  9.950(4), b  18.650(7), c  18.066(6) Å, β  106.81(4)°, Z  4. The two molecules in the asymmetric unit differ slightly in their conformations, both having approximate C₂ symmetry. Bond lengths and angles are: SnSe 2.526 (2.521(3) ? 2.538(3)) Å; SnC 2.138 (2.107(16)?2.168(19)) Å; SnSeSn 103.4(1)°, 105.2(1)°. There are only slight angular distortions at the SnSeC₃ tetrahedra (SeSnC angles: 104.3(5)?114.8(4)°). The bond data indicate essentially single bonds around the Sn atoms.     

Duroquinonerhodium(I) complexes. Crystal structure of [Rh(DQ)(C6H5Me)]PF6

The preparation of cationic arenerhodiiim(I) complexes of the type [Rh(DQ)-(arene)]PF₆ (DQ = duroquinone; arene = C₆H_6-nMe_n, n duroquinone complexes with Group VB donor ligands are described. The crystal structure of [Rh(DQ)(C₆H₅Me)]PF₆ has been determined by X-ray diffraction. The compound crystallizes in the P2₁/n space group, in a unit cell of dimensions a 15.9866(5), b 11.8438(3), c 9.9968(3) Å, β 98.473(4)Å. The structure was solved by Patterson and Fourier methods and refined to R and R_w values of 0.062 and 0.076, respectively. The Rh atom is coordinated to a toluene group (η⁶) and a duroquinone ligand (η⁴), which eclipse each other. Both ligands are distorted to adopt boat-like conformations.