[COH(NH2)2]2[Cu(pic)2(ClO4)2]的合成与晶体结构

The title compound was synthesized by reaction of Cu(ClO₄)₂， picolinic acid and carbamide in C₂H₅OH/CH₃CN solution， and characterized by single-crystal X-ray diffraction. It crystallizes in the orthorhombic system， space group Pbca with a=14.0481(8)， b=9.0130(5)， c=18.626(1)?， V=2358.3(2)?³， Z=4， D_x=1.771g·cm^-3， μ=1.235mm^-1 and F(000)=1276. The final R factor is 0.0440 for 1434 observed reflections. The X-ray analysis revealed that the copper(Ⅱ) atom is coordinated by two picolinic ligands in the equatorial plane， while the two oxygen atoms of perchlorate occupy the axial positions of octahedron with lengthened Cu-O distances， resulting in a 4+2 elongated octahedral environment. In the compound， there also exist two protonated carbamide cations for charge balance. CCDC： 195354.     

Double complex salts [Pd(NH3)4]3[Rh(NO2)6]2, [Pd(NH3)4]3[Rh(NO2)6]2·H2O as promising precursors to prepare Pd-Rh nanoalloys

Two new double complex salts [Pd(NH₃)₄]₃[Rh(NO₂)₆]₂ (I) and [Pd(NH₃)₄]₃[Rh(NO₂)₆]₂·H₂O (II) are synthesized and characterized. The techniques to produce one-phase residues of the salts are developed. The crystallographic data for I: a = 18.915(2) ?, V = 6767.4 ?³, F-43c space group, Z = 8, d _x = 2.548 g/cm³; II: a = 21.160(6) ?, b = 8.085(7) ?, c = 21.363(4) ?, β = 91.71(4)°, V = 3661.1(6) ?³, P2₁/c space group, d _x = 2.357 g/cm³. Thermal properties of the obtained compounds in the hydrogen and helium atmosphere are studied. It is shown that the final product of their decomposition both in the inert and reducing atmosphere is a powder consisting of bimetallic nanosized particles (nanoalloy) of Pd_0.59Rh_0.41 (Fm-3m space group, a = 3.856(2) ?, crystallite size of 8–11 nm).     

Crystal structure of [Pd(NH3)4]3[Ir(NO2)6]2·H2O

A single crystal of [Pd(NH₃)₄]₃[Ir(NO₂)₆]₂·H₂O double complex salt is studied by X-ray diffraction. Crystallographic characteristics are as follows: a = 21.0335(5) ?, b = 8.0592(2) ?, c = 21.3452(5) ?, β = 91.254(1)°, V = 3617.43(15) ?³, P2₁/c space group, Z = 4, d _x = 2.714 g/cm³. Single-layer pseudohexagonal packing of complex anions is determined along the [−1 0 1] direction in the structure. Complex cations and crystallization water molecules are located between the mentioned layers.     

Synthesis, structure, and thermal decomposition of [H2(4,4′-Bipy)][In(H2O)2(NCS)4]2 and [HUr]2[In(H2O)(NCS)5] · 2H2O

The reaction of indium thiocyanate with bipyridine (4,4-Bipy) and urotropine (Ur) gave [H₂(4,4′-Bipy)][In(H₂O)₂(NCS)₄]₂ (I) and [HUr]₂[In(H₂O)(NCS)₅] · 2H₂O (II), which were identified using elemental analysis, IR spectra, and thermogravimetric analysis. The thermal decomposition of compound I and II ends at 650 and 640°C, respectively, and gives In₂O₃. X-Ray diffraction analysis of compound I showed that complex anions in the crystal form chains through O-H…S hydrogen bonds. The anion chains form a close packing of columns with bipyridine cations located in the voids. Original Russian Text ? S.P. Petrosyants, A.B. Ilyukhin, V.A. Ketsko, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 6, pp. 951–955.     

Thiolate-bridged Trinuclear Heterobimetallic Complexes [Cd(μ-SPh-4-Me)4{M(PPh3)2}2] (M?=?Cu, Ag) and [Sn(μ-SPh)6(AgPPh3)2]

Abstract  

Reaction of the [Me₄N]₂[Cd(SPh-4-Me)₄] with two equivalents of [M(PPh₃)₂NO₃] afforded the neutral linear trinuclear complexes [Cd(μ-SPh-4-Me)₄{M(PPh₃)₂}₂] (M = Cu 1, Ag 2) in which two [M(PPh₃)₂]⁺ fragments chelate with the opposite edges of a tetrahedral [Cd(SPh-4-Me)₄]²⁻ moiety via the sulfur atoms of the Me-4-PhS⁻ species. Treatment of [Sn(SPh)₄] with two equivalents of [Ag(PPh₃)₂NO₃] gave the neutral linear trinuclear complex [Sn(μ-SPh)₆(AgPPh₃)₂] (3) that is composed of a central distorted SnS₆ octahedron sharing two opposite planes with two slightly distorted AgS₃P tetrahedrons. Complexes 2 and 3 are air and optically stable. Their nonlinear optical absorption and refraction were investigated under the same conditions. The nonlinear optical absorption and refraction of complex 2 were determined to be α ₂ = 3.11 × 10⁻¹¹ m/W and n ₂ = 4.15 × 10⁻¹² esu, respectively. The nonlinear optical absorption and refraction of complex 3 were determined to be α ₂ = 8.36 × 10⁻¹¹ m/W and n ₂ = 1.47 × 10⁻¹¹ esu, respectively.     

[Ni(dien)2]2[Mn(NCS)6]·H2O的合成、晶体结构

The crystal of [Ni(dien)₂]₂[Mn(NCS)₆]·H₂O was synthesized and the structure of its single crystal was determined by X-ray diffraction. The crystal is monoclinic system, space group P2₁/c with a=16.544(3),b=15.137(2), c=17.334(3)?, β=99.90(1)°, V=4276.3(12)?³, Z=4, D_c=1.479g·cm^-3, M_r=951.55, F(000)=1998, μ=1.489mm^-1, R=0.0399, R_w=0.0958. IR was also determined.     

Dimolybdenum Complex Containing N–H···Mo Interactions. Synthesis and Structure of cis-[Mo2(HDpyF)2(CH3CN)4](BF4)4 and its Transformation to [Mo2(DpyF)2(py)4](BF4)2 [HDpyF?=?Bis(2-pyridyl)formamidine; py?=?pyridine]

The complex cis-[Mo₂(HDpyF)₂(CH₃CN)₄](BF₄)₄, 1, was prepared by the reaction of Mo₂(DpyF)₄ with HBF₄ in CH₃CN, in which new bonding mode of the HDpyF ligand and axial N–H···Mo interactions are observed. Reaction of 1 with pyridine afforded the complex trans-[Mo₂(DpyF)₂(py)₄](BF₄)₂, 2. In complex 1, the neutral bidentate HDpyF ligands bridge the metal centers through one of the amine nitrogen atoms and the adjacent pyridyl nitrogen atom, resulting in the s-trans-anti-s-trans conformation. The anionic DpyF⁻ ligands of 2 adopt the s-trans,s-trans conformation and are coordinated to the Mo centers in bidentate fashions through the two central nitrogen atoms and the two terminal nitrogen atoms are not coordinated. Dedicated to the memory of Professor F. A. Cotton, a great mentor and friend.     

蝎型铜配合物：Cu2[ μ-pz]2[HB(pz)3]2和Cu[B(pz)4]2的合成、结构及热分解动力学性质

本文设计合成了两种以聚吡唑硼酸盐、吡唑为配体的铜配合物Cu₂[ μ-pz]₂[HB(pz)₃]₂(1)和Cu[B(pz)₄]₂(2)(pz：吡唑(C₃H₄N₂))。运用元素分析、红外光谱对配合物进行了表征，并用X-ray衍射测定了它们的晶体结构。非等温热分解动力学研究表明：配合物1的热分解反应分两步，配合物2的热分解反应一步进行。通过计算，配合物1热分解的第一步反应的可能机理为成核与生长，n=1/4；第二步反应的可能机理为化学反应。其非等温动力学方程分别为：dα/dT=A/β e^-E/RT·1/4(1-α)[-ln(1-α)]^-3和dα/dT=A/β e^-E/RT·(1-α)²。分解反应的表观活化能分别是520.37 kJ·mol^-1和149.65 kJ·mol^-1；指前因子lnA分别是118.06 s^-1和28.10 s^-1。配合物2热分解的可能机理为化学反应。其非等温动力学方程为：dα/dT=A/β e^-E/RT·(1-α)²。分解反应的表观活化能是111.41 kJ·mol^-1；指前因子lnA是21.20 s^-1。     

Self-assembly and crystal structures of two heteronuclear complexes with [Ag2(μ-dppm)2(MeCN)2](SbF6)2 and [Bu4N]2[M(mnt)3] (M=Mo, W) as components

Two heteronuclear complexes Mo₂Ag₄(μ-dppm)₄(mnt)₆ · 6MeCN (1) and WAg₂(μ-dppm)₂(mnt)₃ · MeCN (2) were synthesized by self-assembly with [Ag₂(μ-dppm)₂(MeCN)₂](SbF₆)₂ and [Bu₄N]₂[Mmnt)₃] (M=Mo or W, dppm=bis(diphenylphosphino)methane, mnt²⁻ = cis-1,2-dicyanoethylene-1,2-dithiolate) as components and characterized by IR spectra, elemental analysis, ¹H NMR spectra, ³¹P NMR spectra and u.v.–vis spectra. The crystal structures of the two complexes were determined by X-ray analysis.     

The orthopalladation dinuclear [Pd(L1)(μ-OAc)]2, [Pd(L2)(μ-OAc)]2 and mononuclear [Pd(L3)2] complexes with [N, C, O] or [N, O] containing ligands: Synthesis, spectral characterization, electrochemistry and catalytic properties

Treatment of the salicylaldimine ligands (L₁H, L₂H, L₃H, L₄H and L₅H) with palladium(II) acetate in absolute ethanol gave the orthopalladation dinuclear [Pd(L₁)(μ-OAc)]₂, [Pd(L₂)(μ-OAc)]₂ and mononuclear [Pd(L₃)₂] with the tetradentate ligands [N, C, O] or [N, O] moiety. The ligands L₁H and L₂H are coordinated through the imine nitrogen and aromatic ortho carbon atoms, whereas the ligand L₃H coordinated through the imine nitrogen and phenolic oxygens atoms. The Pd(II) complexes have a square-planar structure and were found to be effective catalysts for the hydrogenation of both nitrobenzene and cyclohexene. These metal complexes were also tested as catalysts in Suzuki-Miyaura coupling of aryl bromide in the presence of K₂CO₃. The catalytic studies showed that the introduction of different groups on the salicyl ring of the molecules effected the catalytic activity towards hydrogenation of nitrobenzene and cyclohexene in DMF at 25 and 45 °C. The Pd(II) complexes easily prepared from cheap materials could be used as versatile and efficient catalysts for different C-C coupling reactions (Suzuki-Miyaura reactions). The structure of ligands and their complexes was characterized by UV-Vis, FT-IR, ¹H and ¹³C NMR, elemental analysis, molar conductivity, as well as by electrochemical techniques.     

Synthesis and characterization of [MCl2(nPr-N(Ph2P)2] (M?=?Pt, Pd) complexes and hydroformylation of 1-octene using [PtCl2(R-N(Ph2P)2)] (R?=?benzyl, 2-picolyl, nPr) complexes

The synthesis and characterization of platinum(II) and palladium(II) complexes of the type [PtX₂( ⁿ Pr-N(Ph₂P)₂)] (X = Cl, I) and [PdCl₂(R-N(Ph₂P)₂)] {R =  ⁿ Pr, p-OMe(C₆H₄)} containing aminodiphosphine P,P-bidentate ligands is described. Complexes of the type [PtCl₂(R-N(Ph₂P)₂)] (where R = benzyl, 2-picolyl and ⁿ Pr) catalyzed the hydroformylation of 1-octene, albeit at low activities and slightly elevated regioselectivities toward the linear aldehyde, when compared with analogous compounds containing small bite angles.     

Functionalised tetraarylstannanes Sn[C6H4-R]4 (R=-CH(CH2O)2, -CHO, -COOH, -CHN-NH-C6H3-2,4-(NO2)2, -CH2OH, -CO-NH-CH2-COO-CH3, -CH[N(C2H4)2O]2)

Reaction of tin tetrachloride with the appropriate Grignard reagent gave Sn[C₆H₄-CH(OCH₂)₂]₄ (2), which was transformed to Sn[C₆H₄-CHO]₄ (3) and its hydrazido and amino derivatives Sn[C₆H₄-CHN-NH-C₆H₃-2,4-(NO₂)₂]₄ (5) and Sn{C₆H₄-CH[N(C₂H₄)₂O]₂}₄ (8). Oxidation of (3) produced Sn[C₆H₄-COOH]₄ (4) while reduction of (3) gave Sn[C₆H₄-CH₂-OH]₄ (6). From the acid 4, an amino acid Sn[C₆H₄-CO-NH-CH₂-CO-OCH₃]₄ (7) could be obtained by reaction with the methyl ester of glycine. All compounds were isolated in pure form with yields of 40-64% and were characterised by spectroscopic means (heteronuclear NMR) or by X-ray structure determination (3).     

Synthesis, structure, and characterization of a 1D monocopper substituted Dawson-type arsenotungstate (H2En)0.5[Cu(En)2]0.5{[Cu(En)2(H2O)]2[Cu(En)2] (α1-As2W17CuO61)} · 8H2O

A new 1D organic-inorganic hybrid monocopper substituted Dawson-type arsenotungstate (H₂En)_0.5[Cu(En)₂]_0.5{[Cu(En)₂(H₂O)]₂[Cu(En)₂](α₁-As₂W₁₇CuO₆₁)} · 8H₂O (I) has been hydrothermally synthesized by the reaction of Na₈[A-α-HAsW₉O₃₄] · 11H₂O, CuCl₂ · 2H₂O, YCl₃, with enthylenediamine (En) and characterized by elemental analyses, IR spectra, UV spectra, powder X-ray diffraction, thermogravimetric analysis, as well as single-crystal X-ray diffraction. Single-crystal structural analysis shows that I displays an interesting 1D chain constructed from [α₁-As₂W₁₇CuO₆₁]⁸⁻ subunits by means of common oxygen atoms and [Cu(En)₂]²⁺ bridges. It should be noted that the structural transformation of the trivacant Keggin polyoxoanion [A-α-AsW₉O₃₄]⁹⁻ to the monovacant Dawson [α-As₂W₁₇O₆₁]¹⁰⁻ polyoxoanion was observed. The TG curve of I exhibits three stages of weight loss.     

两个含有平行交替链的新型二氰胺配位高聚物: {Mn(dmpz)[N(CN)2]2}2和{Cu(dmpz)[N(CN)2]2}2

Two new dicyanamide coordination polymers, {Mn(dmpz)[N(CN)2]2}2 (1) and {Cu(dmpz)[N(CN)2]2}2 (2)(dmpz=3,5-dimethylpyrazole), were synthesized and characterized by single crystal X-ray diffraction analysis and IR spectroscopy. In 1 and 2 the metal ions have two different coordination modes, where one is coordinated to four dicyanamide anions and two monodentate dmpz molecules to form a slightly distorted octahedral geometry, while the other adopts octahedral geometry, surrounded by four nitrile N atoms and two amide N atoms of the dicyanamide anions. Both complexes contain two alternating chains that are parallel to each other.     

Molybdenum(VI) imido complexes: formation of [Mo(NPh)(S2CNR2)3]X and [Mo(NPh)(S2CNR2)2(μ-MoO4)]2 (R?=?Me, Et) from the reaction of [MoO2(S2CNR2)2] and PhNCO under aerobic conditions

Abstract  

Products from the thermolysis of PhNCO and [MoO₂(S₂CNR₂)₂] (R = Me, Et) are highly dependent upon the reaction conditions. When carried out in air, the major products are cations, [Mo(NPh)(S₂CNR₂)₃]⁺, as shown by a crystal structure of [Mo(NPh)(S₂CNEt₂)₃]₂[Mo₆O₁₉]. Under rigorously anaerobic conditions, reaction of two equivalents of PhNCO with [MoO₂(S₂CNR₂)₂] affords [Mo(NPh)₂(S₂CNR₂)₂] as the major product. However, chloroform solutions of the bis(imido) complexes hydrolyze in air to afford [Mo(NPh)(S₂CNR₂)₂(μ-MoO₄)]₂, in which molybdate groups bridge between molybdenum(VI) imido-bis(dithiocarbamate) centers. These results are placed in context of our earlier studies of these reactions that lead to the formation of oxo-disulfide [MoS₂(NPh)(S₂CNR₂)₂] and dimeric molybdenum(V) [MoO(μ-NPh)(S₂CNR₂)]₂ complexes, thus allowing a full picture of these transformations to be established.     

Synthesis and structure of [Ni(dien)2]3[W4S4(CN)2]·20H2O and [Cu(dien)(Hdien)]2[W4S4(CN)12]·8H2O

[Ni(dien)₂]₃[W₄S₄(CN)₁₂]·20H₂O and [Cu(dien)(Hdien)]₂[W₄S₄(CN)₁₂]·8H₂O were obtained by evaporating water-ammonia solutions containing K₆[W₄S₄(CN)₁₂]·2H₂O·2CH₃OH, diethylene triamine, and NiCl₂·6H₂O or CuCl₂·6H₂O. The crystals of the complex compounds were obtained within 3 days. The complex compounds were characterized by IR spectroscopy and by XRD and elemental analysis. XRD data for the complex [Ni(dien)₂]₃[W₄S₄(CN)₁₂]·20H₂O are: triclinic system, , a = 14.671(2) Å, b = 16.448(3) Å, c = 19.814(3) Å, α = 67.841(3)°, β = 68.996(3)°, γ = 67.527(3)°, V = 3961.6(11) ų, Z = 2; for the complex [Cu(dien)(Hdien)]₂[W₄S₄(CN)₁₂]·8H₂O: monoclinic system, C2/c, a = 37.4290(1) Å, b = 17.7370(1) Å, c = 25.7370(2) Å, β = 105.3840(2)°, V = 16474.02(16) ų, Z = 12. Original Russian Text Copyright ? 2005 by I. V. Kalinina, D. G. Samsonenko, Z. A. Starikova, A. A. Korlyukov, J. Lipkowski, V. P. Fedin, and M. Yu. Antipin __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 1, pp. 139–148, January–February, 2005.     

Synthesis,structure characterization and thermal properties of [Zr6(μ3-O)4(μ3-OH)4(OOCCH2Bu)9(μ2-OH)3]2

Oxo/hydoxo zirconium(IV) complex of the general formula [Zr₆(μ₃-O)₄(μ₃-OH)₄(OOCCH₂^tBu)₉(μ₂-OH)₃]₂ has been isolated, when Zr(OⁱPr)₄ reacted with a 2-fold excess of 3,3-dimethylbutyric acid. Single crystal X-ray diffraction data, collected at 103 and 153 K, showed that the studied compound crystallizes in hexagonal system (P6₃/m (no. 176)). Structure consists of dimers composed of [Zr₆(μ₃-O)₄(μ₃-OH)₄(OOCCH₂^tBu)₉] sub-units, linked by six μ₂-OH bridges. Infrared spectroscopic studies proved the presence of hydroxo groups in the structure of studied clusters and formation of different types of oxo/hydroxo bridges. The application of variable temperature infrared spectroscopy and differential scanning calorimetry revealed that the structure of this complex undergoes the phase transitions at 143–183 and 203–293 K. Comparison of spectral and crystallographic data suggests that these phase transitions might be related to changes in the strength of Zr–O bonds of μ₂-OH bridges linking complex sub-units, and change in symmetry of the crystal lattice (from hexagonal to trigonal). Analysis of thermogravimetric data showed that decomposition of [Zr₆(μ₃-O)₄(μ₃-OH)₄(OOCCH₂^tBu)₉(μ₂-OH)₃]₂ proceeds with complete conversion to ZrO₂ (monoclinic form) between 603 and 803 K.     

Mixed-ligand complexes [Cd(DMSO)5(NCS)][Cr(NH3)2(NCS)4] · 3DMSO and [Mn(DMSO)4(H2O)2][Cr(NH3)2(NCS)4]2 · 6DMSO · 2H2O: Syntheses and crystal structures

New mixed-ligand coordination compounds[Cd(DMSO)₅(NCS)][Cr(NH₃)₂(NCS)₄] · 3DMSO (I) and [Mn(DMSO)₄(H₂O)₂][Cr(NH₃)₂(NCS)₄]₂ · 6DMSO · 2H₂O (II) have been synthesized and studied by IR spectroscopy and X-ray diffraction analysis. The crystals of compound I are monoclinic, a = 14.5275(7), b = 23.1692(11), c = 14.6969(6) ?, β = 97.057(2)°, V = 4909.4(4) ?³, space group P2₁/c, Z = 4, ρ_calcd = 1.507 g/cm³, R = 0.0556. The crystals of compound II are triclinic, a = 11.7784(3), b = 12.1760(3), c = 13.1922(2) ?, α = 85.5420(10)°, β = 87.9000(10)°, γ = 70.3680(10)°, V = 1776.46(7) ?³, space group P , Z = 1, ρ_calcd = 1.444 g/cm³, R = 0.0350. Original Russian Text ? E.A. Gerasimova, T.V. Utkina, E.V. Peresypkina, A.V. Virovets, T.G. Cherkasova, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 5, pp. 751–755.     

Pyridine-2-thione (pySH) derivatives of silver(I): Synthesis and crystal structures of dinuclear [Ag2Cl2(μ-S-pySH)2(PPh3)2] and [Ag2Br2(μ-S-pySH)2(PPh3)2] complexes

Reaction of silver(I) halides with PPh₃ in acetonitrile and then with pyridine-2-thione (pySH) chloroform (1:1:1 molar ratio) has yielded sulfur bridged dimers of general formula, [Ag₂X₂(μ-S-pySH)₂(PPh₃)₂] (X = Cl, 1, Br, 2). Both these complexes have been characterized using analytical data, NMR spectroscopy and single crystal X-crystallography. The central Ag₂S₂ cores form parallelograms with unequal Ag–S bond distances (2.5832(8), 2.7208(11) Å) in 1 and (2.6306(4), 2.6950(7) Å) in 2, respectively. The Ag?Ag contacts of compounds 1 and 2 are 3.8425(8) and 3.8211(4) Å, respectively. The angles around Ag (in the range 87.19(2)–121.71(2)° in 1 and 87.81(2)–121.53(2)° in 2) reveal highly distorted tetrahedral geometry. There are inter dimer π–π stacking interactions between pyridyl rings (inter ring distances of 3.498 and 3.510 Å in complexes 1 and 2, respectively). The solution state ³¹P NMR spectroscopy has shown the existence of both monomers and dimers. The studies reveal relatively weaker intramolecular –NH?Cl hydrogen bonding in case of AgCl vis-à-vis that in CuCl which favored both a monomer and a dimer with AgCl, and only a monomer with CuCl.     

[Cu(Hsal)2(py)2]n晶体结构和二维堆积网络

０引言水杨酸具有羧基和羟基，是双功能基配体，羧基和羟基可分别脱去氢，因此有多种形式可参与配位（见Scheme１），其中Hsal－１的形式仅见一例报道犤１犦，其可靠性有待更多的研究来确证。对铜／水杨酸／吡啶三元体系的研究已有多篇文献报道犤２～４犦，亦有几种化合物合成，例如Cu（Hsal）２（py）２和Cu（sal）（py）２等。配合物Cu（sal）（py）２的可靠性值得怀疑，原文中无合成和表征犤３犦。铜／水杨酸／吡啶衍生物三元体系已有多个晶体结构报道犤５，６犦，但迄今无铜／水杨酸／吡啶三元体系晶体结构报道。对于配合物Cu（Hsal…