Synthesis and Structure of Triphenylbismuth Dicarboxylates Ph3Bi[OC(O)R]2 (R = CH2C6H4F-3, C6H3F2-2,3, C6HF4-2,3,4,5)

Russian Journal of General Chemistry - Bismuth compounds Ph3Bi[OC(O)R]2 (R = CH2C6H4F-3, C6H3F2-2,3, C6HF4-2,3,4,5) were synthesized by the reaction of triphenylbismuth with a carboxylic acid and...     

Triarylantimony Dicaroxylates Ar3Sb[OC(O)R]2 (Ar = Ph,p-Tol; R = 2-C4H3O, 3-C5H4N): Synthesis and Structure

Bis(2-furoinate)triphenyl- and tri-p-tolylantimony and bis(3-niacinate)triphenylanitmony were synthesized by reacting triarylantimony (Ar₃Sb; Ar = Ph, p-Tol) with 2-furancarboxylic and 3-pyridinecarboxylic acids in the presence of hydrogen peroxide. According to X-ray diffraction data, Sb atoms have trigonal bipyramidal coordination polyhedra. The Sb–O distances are 2.117(4), 2.137(4) Å; 2.136(2), 2.158(2) Å, and 2.112(1), 2.101(2) Å, the Sb···O distances are 2.866(4), 2.798(4) Å; 2.816(2), 2.774(2) Å, and 3.054(2), 3.168(2) Å, respectively.     

Synthesis and structure of tris(4-fluorophenylantimony) dicarboxylates: (4-FC6H4)3Sb[OC(O)R]2, R = CH2I,C6F5

Russian Chemical Bulletin - Tris(4-fluorophenyl)antimony reacts with iodoacetic and pentafluorobenzoic acids in the presence of tert-butylhydroperoxide to give tris(4-fluorophenyl)antimony...     

Synthesis,structure and magnetic properties of {Mn5(OC(O)CH3)6(OC(O)C6H5)4}∞

The ligand exchange reaction between Mn(OC(O)CH₃)₂ and benzoic acid under solvothermal conditions in toluene at 110 °C yields colorless crystals of {Mn₅(OC(O)CH₃)₆(OC(O)C₆H₅)₄}_∞ (1). The asymmetric unit of this complex is Mn_2.5(OC(O)CH₃)₃(OC(O)C₆H₅)₂ with each of the three different Mn(II) atoms in 6-fold coordination and one of the benzoate ligands exhibiting the rare μ₃-symmetric bridging mode (O–Mn–O angle = 57°). The structure consists of edge-shared Mn₁₂ loops arranged in a honeycomb-like 2D sheet with the acetate ligands displaced slightly out of the plane. The sheets are spaced at 12 Å and linked into a 3D network via weak intersheet interactions. Magnetic susceptibility characterization of 1 indicates antiferromagnetic exchange with a Weiss constant of −165 K and a transition toward ferromagnetic exchange below 10 K corroborated with a finite imaginary component in the variable temperature susceptibility data.     

Synthesis,Structure and Hydrogenation Property of trans-PdCl_2｛Ph_2P[o-C_6H_4CH(OC_2H_5)_2]｝_2

Ｓｙｎｔｈｅｓｉｓ,ＳｔｒｕｃｔｕｒｅａｎｄＨｙｄｒｏｇｅｎａｔｉｏｎＰｒｏｐｅｒｔｙｏｆｔｒａｎｓ┐ＰｄＣｌ２｛Ｐｈ２Ｐ［ｏ┐Ｃ６Ｈ４ＣＨ（ＯＣ２Ｈ５）２］｝２＊ＸＵＰｉａｎ－ｐｉａｎ,ＧＡＯＪｉｎｇ－ｘｉｎｇ＊＊,ＺＨＯＵＺｈａｏ－ｈｕｉ,ＷＡＮ...     

Comparative reactivity of diacetals of the type (C2H5O)2CH(CH2)nCH(OC2H5)2

Summary The reactivity of diacetals in the reaction with vinyl ether in comparison with the diacetal of malonic dialdehyde increases in the following order: diacetal of glyoxal < malonic diacetal < succinic diacetal < glutaric diacetal < adipic diacetal.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 1657–1658, September, 1965     

Synthesis of bisvinylidene complex of manganese Cp (OC)2Mn=C=CHC6H4CH=C=Mn(CO)2 Cp

Russian Chemical Bulletin -     

Synthesis and Crystal Structure of Dinuclear Copper Complex[Cu（CH2O（C6H4）N=C（C6H4）O）（Py]2

1 INTRODUCTION Synthesis of transition metal complexes with Schiff-base has been a subject of considerable importance [1,2]. They are not only good complexing agents for Schiff-base, but also good bactericide and antitumour agent [3,4]. At present, there is a spectacular growth in this field. Recently, some bridged binuclear complexes have received much attention on account of their biological relevance and condensed-phase magnetic properties[5,6]. Especially, the complexes containin…     

Studies on the non-isothermal kinetics of thermal decomposition of the mixed ligand complex — [Fe2O(OC6H4CH=NC6H4O)2(C5H5N)4]·2H2O

The thermal decomposition of the mixed-ligand complex of iron(III) with 2-[(o-hydroxy benzylidene)amino] phenol and pyridine-[Fe₂O(OC₆H₄CH=NC₆H₄O)₂(C₅H₅N)₄]·2H₂O and its non-isothermal kinetics were studied by TG and DTG techniques. The non-isothermal kinetic data were analyzed and the kinetic parameters for the first and second steps of the thermal decomposition were evaluated by two different methods, the Achar and Coats-Redfern methods. Steps 1 and 2 are both second-order chemical reactions. Their kinetic equations can be expressed as: dα/dt=Ae^?E/RT(1-α)²     

〔C_5H_4C(CH_3)_2CH_2CH=CH_2〕Sm(OH)Cl·2MgCl_2·4THF的晶体结构分析

用Ｘ－射线晶体结构衍射法测定了〔Ｃ５Ｈ４Ｃ（ＣＨ３）２ＣＨ２ＣＨ＝ＣＨ２〕Ｓｍ（ＯＨ）Ｃｌ·２ＭｇＣｌ２·４ＴＨＦ的晶体结构。它属三斜晶系,空间群为Ｐ１,ａ＝１０．７７３（２）,ｂ＝１２．８３６（３）,ｃ＝１５．４７８（３）,α＝１１１．４６（３）,β＝１０７．７１（３）,γ＝９２．５４（３）°,Ｖ＝１８６８（１）３,Ｍｒ＝８２７．９１,Ｄｘ＝１．４７２ｇ／ｃｍ３,μ＝２．０００６ｍｍ－１,Ｆ（０００）＝８４０,Ｚ＝２,Ｒ＝０．０４１,ｗＲ＝０．０５０（Ｉ≥３σ（Ｉ））。分子中Ｓｍ原子的配位数为８,形成一个严重扭曲的八面体结构;２个Ｍｇ原子的配位情况相似,它们的配位数都是６,分别构成２个扭曲的八面体。这３个八面体通过３个共平面联接     

Electrosynthesis of Rh2(dpf)4(R) where dpf = N,N'-diphenylformamidinate anion and R = CH3, C2H5, C3H7, C4H9 or C5H11

The electrosynthesis of Rh(2)(dpf)(4)(R) where dpf is the N,N'-diphenylformamidinate anion and R = CH(3), C(2)H(5), C(3)H(7), C(4)H(9) or C(5)H(11) was carried out in THF containing 0.2 M tetra-n-butylammonium perchlorate (TBAP) and one of several alkyl iodides represented as RI. The initial step in the reaction involved a one-electron reduction of the Rh(2)(4+) unit in Rh(2)(dpf)(4) to its Rh(2)(3+) form followed by a homogeneous reaction involving electrogenerated [Rh(2)(dpf)(4)](-) and the alkyl iodide in solution to give Rh(2)(dpf)(4)(R). The homogeneously generated Rh(2)(5+) product was then immediately reduced by a second electron at the potential where [Rh(2)(dpf)(4)(R)](-) is generated, giving [Rh(2)(dpf)(4)(R)](-) which contains a Rh(2)(4+) center as a final product of an electrochemical ECE mechanism. The electrosynthesized [Rh(2)(dpf)(4)(CH(3))](-) derivative could be reoxidized to Rh(2)(dpf)(4)(CH(3)) on the reverse potential sweep and both forms of the CH(3) bonded derivative were in situ characterized by cyclic voltammetry combined with UV-visible and/or ESR spectroscopy. The reversible Rh(2)(4+/3+) process of Rh(2)(dpf)(4) is located at E(1/2) = -1.11 V in THF, 0.2 M TBAP while the electrogenerated Rh(2)(dpf)(4)(R) products are substantially easier to reduce, with E(p) values for the Rh(2)(5+/4+) couples ranging from -0.50 to -0.54 V vs. SCE depending upon the specific R group.     

Reactivity Studies of Iridium Pyridylidenes [TpMe2Ir(C6H5)2(C(CH)3C(R)NH] (R=H,Me, Ph)

The reactivity of a series of iridium? pyridylidene complexes with the formula [Tp^Me2Ir(C₆H₅)₂(C(CH)₃C(R)N H] ( 1 a – 1 c ) towards a variety of substrates, from small molecules, such as H₂, O₂, carbon oxides, and formaldehyde, to alkenes and alkynes, is described. Most of the observed reactivity is best explained by invoking 16 e^? unsaturated [Tp^Me2Ir(phenyl)(pyridyl)] intermediates, which behave as internal frustrated Lewis pairs (FLPs). H₂ is heterolytically split to give hydride? pyridylidene complexes, whilst CO, CO₂, and H₂C?O provide carbonyl, carbonate, and alkoxide species, respectively. Ethylene and propene form five‐membered metallacycles with an IrCH₂CH(R)N (R=H, Me) motif, whereas, in contrast, acetylene affords four‐membered iridacycles with the IrC(?CH₂)N moiety. C₆H₅(C?O)H and C₆H₅C?CH react with formation of Ir? C₆H₅ and Ir? C?CPh bonds and the concomitant elimination of a molecule of pyridine and benzene, respectively. Finally the reactivity of compounds 1 a – 1 c against O₂ is described. Density functional theory calculations that provide theoretical support for these experimental observations are also reported.     

Crystal Structure of Tetrakis (phenacetin) Dihydrogentetraiodide Dihydrate {[H5C2OC6H4N (H)C(CH3)O]4·H2I4·2H2O}

(Phenacetin)₄·₂I₄·2H₂O is triclinic, a = 13.641 (7), b = 12.807 (6), c = 7.201 (3) Å, α = 99.8 (4), b? = 86.5 (4), γ = 104.0 (5)°, P1 , Z = 1. The ordered crystal structure has been refined to R_F = 0.050, using 4173 independent reflections measured on a four-circle diffractometer with MoKa (graphite monochromator) radiation. The crystals are composed of alternating positively and negatively charged slices; each positive slice contains a double layer of stacks of hemi-protonated phenacetin molecules which are H-bonded through their carbonyl groups (d(O - - - O) = 2.432 (4) Å) while each negative slice contains a single layer of I^2?₄-ions linked in chains along [100] through H-bonds to pairs of water molecules. The axes of the phenacetin stacks are parallel to the planes of the (I^2?₄·2H₂O)-layers. The I^2?₄-ion is centro-symmetric and can be approximately represented as I^?- - - I–I- - - I^? (d(I^? - - - I) = 3.404 (1) Å; d(I–I) = 2.774 (1) Å). The compound is a pseudo-type A basic salt.     

[C5H4C(CH3)2CH2CH=CH2]Sm(OH)Cl·2MgCl2·4THF的晶体结构分析

用Ｘ－射线晶体结构衍射法测定了［Ｃ５Ｈ４Ｃ（ＣＨ３）２ＣＨ２ＣＨ＝ＣＨ２］Ｓｍ（ＯＨ）Ｃｌ·２ＭｇＣｌ２·４ＴＨＦ的晶体结构。它属三斜晶系,空间群为Ｐ＾－１,ａ＝１０．７７３（２）,ｂ＝１２．８３６（３）,ｃ＝１５．４７８（３）Ａ,ａ＝１１１．４６（３）,β＝１０７．７１（３）,γ＝９２．５４（３）°,Ｖ＝１８６８（１）Ａ＾３,Ｍｒ＝８２７．９１,Ｄｘ＝１．４７２ｇ／ｃｍ＾３,μ＝２．０００６ｍｍ     

Synthesis and Crystal Structure of Cadmium（Ⅱ） Complex [Cd（H2O）（CH3OC6H4COO）2]n

1 INTRODUCTION Cadmium (Ⅱ) complexes have been exten- sively studied from both chemical and structural views, mainly due to the capability of cadmium (Ⅱ) (shared by most d10 metal ions) to adopt different modes of coordination determined by the consideration of size, as well as electrostatic and covalent bonding forces[1]. And the field of coordination polymers has witnessed tremendous growth over the last decade[2]. Many coordination polymeric networks have been shown to posses intere…     

三苯基锡(Ⅳ)荒酸酯Ph3SnS2CN(C4H8O)的合成、生物活性及晶体结构

吗啉荒酸酯;三苯基锡(Ⅳ)荒酸酯Ph3SnS2CN(C4H8O)的合成、生物活性及晶体结构     

Substituted N-picolylethylenediamines of the type (ArNHCH2CH2){(2-C5H4N)CH2}NR [R = Me, 4-CH2=CH(C6H4)CH2, (2-C5H4N)CH2] and their transition metal(II) halide complexes

Alkylation of (ArNHCH2CH2){(2-C5H4N)CH2}NH with RX [RX = MeI, 4-CH2=CH(C6H4)CH2Cl) and (2-C5H5N)CH2Cl] in the presence of base has allowed access to the sterically demanding multidentate nitrogen donor ligands, {(2,4,6-Me3C6H2)NHCH2CH2}{(2-C5H4N)CH2}NMe (L1), {(2,6-Me3C6H3)NHCH2CH2}{(2-C5H4N)CH2}NCH2(C6H4)-4-CH=CH2 (L2) and (ArNHCH2CH2){(2-C5H4N)CH2}2N (Ar = 2,4-Me2C6H3 L3a, 2,6-Me2C6H3 L3b) in moderate yield. L3 can also be prepared in higher yield by the reaction of (NH2CH2CH2){(2-C5H4N)CH2}2N with the corresponding aryl bromide in the presence of base and a palladium(0) catalyst. Treatment of L1 or L2 with MCl2 [MCl2 = CoCl2.6H2O or FeCl2(THF)1.5] in THF affords the high spin complexes [(L1)MCl2](M = Co 1a, Fe 1b) and [(L2)MCl2](M = Co 2a, Fe 2b) in good yield, respectively; the molecular structure of reveals a five-coordinate metal centre with bound in a facial fashion. The six-coordinate complexes, [(L3a)MCl2](M = Co 3a, Fe 3b, Mn 3c) are accessible on treatment of tripodal L3a with MCl2. In contrast, the reaction with the more sterically encumbered leads to the pseudo-five-coordinate species [(L3b)MCl2](M = Co 4a, Fe 4b) and, in the case of manganese, dimeric [(L3b)MnCl(mu-Cl)]2 (4c); in 4a and 4b the aryl-substituted amine arm forms a partial interaction with the metal centre while in 4c the arm is pendant. The single crystal X-ray structures of , 1a, 3b.MeCN, 3c.MeCN, 4b.MeCN and 4c are described as are the solution state properties of 3b and 4b.     

Molecular and crystal structures of Ph2P(O)(CH2)2OH and Ph2P(O)CH2(C6H6)OH

The molecular and crystal structures of Ph₂P(O)(CH₂)₂OH and Ph₂P(O)CH₂(C₆H₆)OH have been determined. For the first compound the space group is with unit cell dimensions a=10.505(2), b=13.720(2), c=14.782(3) Å; =72.58(6), =76.95(6), =72.49(6)° for Z=6 (Syntex diffractometer,MoK radiation, 2996 reflections, R=3.2%). The second compound crystallizes in the space group P2₁2₁2₁ with unit cell dimensions a=9.371(3), b=9.014(3), c=18.461(5) Å for Z=4 (DAR-UM diffractometer,CuK radiation, 909 reflections, R=4.9%). In Ph₂P(O)(CH₂)₂OH, three independent molecules differing in structural details are linked by the P=O...O hydrogen bonds (O...H is 1.84, 1.80, and 1.86 Å), to form a chain. In Ph₂P(O)CH₂(C₆H₆)OH, the molecules are joined by pairs of the P=O...H–O bonds (O...H is 1.81 Å) to form 16-membered dimeric associates.Institute of Chemical Physics, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 34, No. 3, pp. 109–118, May–June 1993.Translated by T. Yudanova     

Conformations produced by interactions of the side chains in poly(silylenemethylene) with the repeating sequence [Si(CH3)R?CH2]x [R = ?O(CH2)3OC6H4C6H5]

A coarse-grained model has been developed for asymmetrically substituted poly(silylenemethylene)s in which the side chain is a flexible spacer terminated by a biphenyl unit. Each monomer unit is represented by four coarse-grained beads that interact via a Lennard–Jones potential and are subject to the first- and second-order interactions deduced from the atomistically detailed model. Metropolis Monte Carlo simulations were performed for isolated syndiotactic, isotactic, and atactic chains. Snapshots from the equilibrated coarse-grained chain on the discrete space of a high coordination lattice were reverse-mapped to atomistically detailed structures in continuous space. At 373 K, the chains were disordered independent of the stereochemical composition. The occupancy of bond pairs depended on the stereochemical composition, with the trans-gauche (tg) sequence being favored by the isotactic chain. When the simulation was performed with the backbone constrained to specific periodic structures, the g helix was the lowest energy structure for either the atactic or isotactic chains. For the syndiotactic chain, the g and gt helices were favored. The appearance of the g helix as the favored periodic structure of the isolated chain was consistent with the chain conformation reported previously for the smectic phase of this polymer in the bulk state. The g helix was disrupted when the backbone was allowed to access nonhelical conformations, even though these conformations may have been slightly higher in energy. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 886–896, 2005