Synthesis of solvates of the copper(II) complex with chiral caryophyllane-type morpholino oxime (HL). Structure of Cu(HL)Cl<Subscript>2</Subscript> · CHCl<Subscript>3</Subscript>

Paramagnetic Cu(HL)Cl₂ · 0.25CHCl₃ (I) and Cu(HL)C1₂ · 0.25CH₂C1₂ (II), where HL is the optically active morpholino oxime obtained from the terpenoid caryophyllene, were synthesized. The crystals of Cu(HL)Cl₂ · CHCl₃ (III) were isolated. According to X-ray diffraction data, the crystals of III are composed of acentric mononuclear complex molecules Cu(HL)Cl₂ and solvate molecules CHCl₃. In the complex molecules, the Cu ion coordinates two N atoms of the bidentate chelating ligand HL and two C1 atoms at the vertices of a distorted tetrahedron. The translationally identical molecules of the complex combined by H-bonds form chains along the axis x.     

Synthesis and DFT calculations of oxido and phenylimido-rhenium(V) complexes incorporating the N,O donor ligand 2-[(2-hydroxyethylimino)methyl]phenol

The reactions of equimolar amounts of trans-[ReOC1₃(PPh₃)₂] or trans-[Re(NPh)(PPh₃)₂Cl₃] with a Schiff base formed by condensation of 2-hydroxy-4-methoxybenzaldehyde and ethanolamine (H₂L) result in the formation of cis-[ReO(HL)PPh₃Cl₂] (1a) and trans-[Re(NPh)(HL)(PPh₃)Cl₂] (2b), respectively, in good yields. 1a and 2b have been characterized by a range of spectroscopic and analytical techniques. The X-ray crystal structures of 1a and 2b reveal that 1a is an octahedral cis-Cl,Cl oxorhenium(V) complex, while 2b is a trans-Cl,Cl phenylimidorhenium(V) complex. The complexes are weakly emissive at room temperature with quantum yields of 10^?4. Density functional theory calculations of the electronic properties of the complexes were performed and are in agreement with the experimental results. The complexes display quasi-reversible Re(V)/Re(VI) redox couples in acetonitrile. There is reasonable agreement between the experimental and calculated redox potentials of 1a and 2b.     

Zinc complexes with 1-(1H-benzimidazol-1-ylmethyl)-1H-benzotriazole: the structure,quantum chemical calculations,and luminescence properties

An organic ligand 1-(1H-benzimidazol-1-ylmethyl)-1H-benzotriazole (bta) and two zinc complexes of the composition [Zn(bta)₂Hal₂] (Hal = Cl, Br) were synthesized. The crystal structure of the complex [Zn(bta)₂Cl₂] was determined and its features were discussed. According to X-ray diffraction data, the central atom has a tetrahedral environment composed of two nitrogen atoms from two ligand molecules coordinated in monodentate mode and two terminal chloride ions. Density functional theory (DFT) calculations of the ligand and complex [Zn(bta)₂Cl₂] were carried out. A study of the luminescence properties of the compounds synthesized suggests that excitation of the zinc complexes gives rise to a dual-band luminescence similar to that of the free ligand. Most probably, the emission originates from π—π* and π—π* intra-ligand transitions.

     

Binuclear Pd(II) complexes with chiral ethylenediaminodioxime (H2L) and bis-α-thiooxime (H2L1), the derivative of monoterpenoid(+)-3-carene. Crystal structures of [Pd2(H2L)Cl4] and [Pd2(H2L1)Cl4] · 3CDCl3

Diamagnetic Pd(II) complexes with the chiral ethylenediaminodioxime (H 2 L) and bis-α-thiooxime (H₂L¹), the derivatives of monoterpenoid (+)-3-carene, of the composition Pd₂(H₂L)Cl₄(I), Pd₂(H₂L¹)Cl₄ (II), and the solvate Pd₂(H₂L¹)Cl₄·3DCl₃ (III) were synthesized. The crystal structures of complex I and solvate III were determined from X-ray diffraction data. The structures consist of acentric binuclear molecules with the coordination cores PdN₂Cl₂ (in I) and PdNSCl₂ (in III) in the form of the distorted squares. In complex I, each Pd atom coordinates two N atoms of the tetradentate bridge-cyclic ligand H₂L and two Cl atoms; in compound III, one N and one S atom of the tetradentate bridge-cyclic ligand H₂L¹, and 2 Cl atoms. The CDCl₃ molecules in compound III lie in the cavities formed by the molecules of complex II. In both structures, the PdCl₂ fragments are in the trans-positions. The ¹H NMR spectra indicate that the structures of complexes I, II in solutions are similar to the structures of compounds I, III in the solid state. Original Russian Text ? T.E. Kokina, L.I. Myachina, L.A. Glinskaya, A.V. Tkachev, R.F. Klevtsova, L.A. Sheludyakova, S.N. Bizyaev, A.M. Agafontsev, N.B. Gorshkov, S.V. Larionov, 2008, published in Koordinatsionnaya Khimiya, 2008, Vol. 34, No. 2, pp. 120–132.     

Synthesis and structure of tin tetrachloride adducts with crown ether: Crystal structure of [Sn(H2O)2Cl4] · 18C6 and [Sn(H2O)2Cl4] · 18C6 · 2H2O

Tin coordination compounds [Sn(H₂O)₂Cl₄] · 18C6 (I) and [Sn(H₂O)₂Cl₄] · 18C6 · 2H₂O (II) were synthesized and identified by IR spectroscopy, CH analysis, and X-ray powder diffraction. The crystal structures of compounds I and II were determined. The crystals of I and II are orthorhombic; a = 16.871(1) ?, b = 7.7305(7) ?, c = 16.939(1) ?, Z = 4, space group Cmca for I; a = 14.206(2) ?, b = 20.376(3) ?, c = 8.319(1) A, Z = 4, space group Pna21 for II. The structural units of I and II are [Sn(H₂O)₂Cl₄] · 18C6 complex molecules (in II, also water molecules of crystallization). The coordinated water molecules in I are trans and those in II are cis to each other. The structural units in the crystals of I and II are combined only by hydrogen bonds between water molecules and the crown-ether oxygen atoms with the formation of the chain structure. Complex I was tested as the precursor of tin dioxide in a chemical vapor deposition (CVD) process. The morphology of the obtained film was studied by atomic force microscopy (AFM) and scanning electron microscopy (SEM), and the composition was studied by laser mass spectrometry for elemental analysis.     

The first coordination compounds of OP[NC4H8O]3 phosphoric triamide ligand: structural study and Hirshfeld surface analysis of SnIV and MnII complexes

The first X-ray crystal structures of coordination compounds of OP[NC₄H₈O]₃ phosphoric triamide (L) are investigated in Cl₂(CH₃)₂Sn(trans-L)₂ (1) and [Mn(H₂O)₄(trans-L)₂]Cl₂·2H₂O (2) as models of molecular and salt complexes for Hirshfeld surface (HS)-based analysis. The crystal packing of 1 includes weak interactions, while in the salt complex 2, a 2-D aggregate, along the (001) plane, is mediated by normal O–H?Cl and O–H?O hydrogen bonds. In the Hirshfeld study, the crystal cohesions of 1 and 2 are recognized via H?H, O?H/H?O, and Cl?H/H?Cl contacts. Among these interactions, hydrogen bonds O–H?Cl occur in the salt structure of 2, as well as some weaker hydrogen interactions as C–H?O (1 and 2), C–H?Cl (1), and O–H?O (2). The full fingerprint plots have nearly symmetric shapes for two independent molecules of 1, while an asymmetric shape appears for the cationic component of 2. To extract more detailed information on close intermolecular contacts, the molecular surface of the previously reported structure L was also mapped. The structure 2 is the first monomeric octahedral Mn(II)–phosphoric triamide complex reported so far. Furthermore, the HS analysis of 2 is the first such study on a cation–anion complex structure including phosphoric triamide ligand.     

Chiral complexes of PdCl<Subscript>2</Subscript> with hydroxypyrazolylquinoline and pyrazolylquinoline based on the monoterpenoid (+)-3-carene: Synthesis and structures

The chiral complexes [PdL¹Cl₂] (I) and [PdL²Cl₂] (II) (where L¹ and L² are hydroxypyrazolylquinoline and pyrazolylquinoline, respectively, based on the monoterpenoid (+)-3-carene) were obtained and examined using X-ray diffraction. The crystal structures of complexes I and II are built from mononuclear acentric molecules. The Pd²⁺ ions coordinate two N atoms of the chelating bidentate ligand L¹ or L² and two Cl atoms. The coordination polyhedron Cl₂N₂ is a square distorted in a tetrahedral manner. In structure I, adjacent molecules are linked by intermolecular contacts and hydrogen bonds Cl···H-O, which gives rise to chains aligned with the axis x. In structure II, contacts that are substantially shorter than the van der Waals interactions were not detected.     

Aggregation of two different coordination polymers by reacting zinc nitrate and cadmium chloride with N,N′-ethylenebisacetamide

Two different coordination polymers are obtained from d¹⁰ metal ions [Zn(II) and Cd(II)] and N,N′-ethylenebisacetamide (EBA). {[Zn(EBA)_1.5(NO₃)]?·?(NO₃)} _n (1) is a 1-D coordination polymer assembled from zinc ions and EBA molecules acting as a bridging ligand. Cd(H₂O)₂Cl₂(EBA) (2) is constructed from 1-D inorganic polymeric chains {Cd(OH₂)₂Cl₂} _n and uncoordinated N,N′-ethylenebisacetamide molecules. These chains are interconnected through hydrogen bonds resulting in a 3-D supramolecular network. The luminescent properties of the organic molecule EBA, as well as of the coordination polymers 1, and 2 have been investigated.     

Destruction of the propylenediamine ring upon the chlorination of the platinum(IV) tetramine complex [PtpnPy2Cl2]Cl2

The chlorination of an aqueous solution of [PtpnPy₂Cl₂]Cl₂ affords the platinum(IV) dichloroamine complex [PtPy₂(NCl₂)₂Cl₂](I), as the major reaction product formed due to the complete destruction of the five-membered chelate ring. Complex I is obtained in the pure state from acetonitrile. In addition, the [PtPy(NH₂-CH(CH₃)-CH(CH₃)-NH₂)Cl₃]Cl · 1/2 H₂O complex (II) is isolated from the mother liquor upon chlorination. Complex I reacts rapidly with concentrated HCl to form the tetramine complex [PtPy₂(NH₃)₂Cl₂](CF₃SO₃)₂ · 1/2 H₂O(III). The X-ray diffraction study is carried out for complexes I, II, and III. Complex I crystallizes in the monoclinic crystal system: space group C2/c, a = 7.4529(4), b = 15.2143(9), c = 14.9965(8) Å, β = 99.866(1)°, V = 1675.3(2) ų, Z = 4; R _hkl = 0.040. The crystals of complex II are triclinic: space group P $ \bar 1 The chlorination of an aqueous solution of [PtpnPy₂Cl₂]Cl₂ affords the platinum(IV) dichloroamine complex [PtPy₂(NCl₂)₂Cl₂](I), as the major reaction product formed due to the complete destruction of the five-membered chelate ring. Complex I is obtained in the pure state from acetonitrile. In addition, the [PtPy(NH₂-CH(CH₃)-CH(CH₃)-NH₂)Cl₃]Cl · 1/2 H₂O complex (II) is isolated from the mother liquor upon chlorination. Complex I reacts rapidly with concentrated HCl to form the tetramine complex [PtPy₂(NH₃)₂Cl₂](CF₃SO₃)₂ · 1/2 H₂O(III). The X-ray diffraction study is carried out for complexes I, II, and III. Complex I crystallizes in the monoclinic crystal system: space group C2/c, a = 7.4529(4), b = 15.2143(9), c = 14.9965(8) ?, β = 99.866(1)°, V = 1675.3(2) ?³, Z = 4; R _hkl = 0.040. The crystals of complex II are triclinic: space group P , a = 8.163(2), b = 8.656(2), c = 10.638(2) ?, α = 78.30(3)°, β = 83.95(3)°, γ = 84.68(3)°, V = 730.0(3) ?³, Z = 2; R _hkl = 0.026. The crystals of complex III are monoclinic: space group C2/c, a = 11.946(2), b = 19.624(4), c = 10.034(2) ?, β = 95.96(3)°, V = 2339.5(8) ?³, Z = 4; R _hkl = 0.043. The IR spectra of all the compounds synthesized are studied. Original Russian Text ? I.B. Baranovskii, M.D. Surazhskaya, M.A. Golubnichaya, G.G. Aleksandrov, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 12, pp. 2000–2007.     

Inclusion Compounds of Cyclotriveratrylene (2,3,7,8,12,13-hexamethoxy-5,10-dihydro-15H-tribenzo[a,d,g]cyclononene) with Chlorinated Guests

Inclusion compounds were formed between the host cyclotriveratrylene, H, (2,3,7,8,12,13-hexamethoxy-5,10-dihydro-15H-tribenzo[a,d,g]cyclononene) and the guests carbon tetrachloride, 1,1,1-trichloroethane, 1,1,1-trichloropropane and 1,1,2-trichloroethane. 1 (H·CCl₄) has guest molecules in channels alternating with channels of host molecules. 2 (H·C₂H₃Cl₃·C₃H₅Cl₃) and 3 (H·2C₂H₃Cl₃) exhibit a slightly different packing arrangement with one guest molecule in the host cavity and the rest of the guest molecules in channels. The stability and reactivity of these inclusion compounds were investigated.     

酰腙类Schiff碱汞(Ⅱ)配合物的合成及晶体结构

合成了Schiff碱配体3-乙酰吡啶缩邻氨基苯甲酰腙(L¹)及4-乙酰吡啶缩邻氨基苯甲酰腙(L²),并分别与HgCl₂进行了配位反应,得到2个配位聚合物{[Hg(L¹)Cl₂]·CH₃OH}_n (1)和[Hg(L²)Cl₂]_n (2),采用¹H NMR、FTIR和元素分析等手段对化合物进行了表征,并对配合物的热稳定性进行了考察。通过X射线单晶体衍射技术测定了2个配合物的单晶结构,结构解析表明,配合物1属于三斜晶系,P1空间群,配合物2属于单斜晶系,P2₁/n空间群。     

Synthesis of Pd(II) complexes containing the protonated form or molecule of 2-(3,5-dimethylpyrazol-1-yl)-4-methylquinoline (L). The crystal structure of [Pd(HL)Cl<Subscript>3</Subscript>]

The diamagnetic complexes [Pd(HL)Cl₃](I) and PdLCl₂(II), where L is 2-(3,5-dimethylpyrazol-1-yl)-4-methylquinoline, were obtained. According to X-ray diffraction data, the crystal structure of complex I consists of mononuclear acentric molecules. The coordination polygon PdNCl₃ is a distorted square (trapezium) made up of the pyrazole N atom of the monodentate ligand (cation HL⁺) and three Cl atoms. Complex II seems to contain the square polygon PdN₂Cl₂.     

Interaction Between Pd(RaaiR′)Cl<Subscript>2</Subscript> and Adenine: Reaction Dynamics and Mechanism [RaaiR′ = 1-alkyl-2-(arylazo)imidazole]

Nucleophilic substitution of Pd(RaaiR′)Cl₂ [RaaiR′=1-alkyl-2-(arylazo)imidazole, p-R—C₆H₄— N=N—C₃H₂NN-1-R′; where R= H(a)/Me(b)/Cl(c) and R′ = Et(1)/Bz(2)] with adenine (A) in MeCN–water (1:1) at 298 K, to form [Pd(A)₂]Cl₂, has been studied spectrophotometrically under pseudo-first-order conditions and the analyses support a nucleophilic association path. The reaction follows the rate law, rate = {a+k [A] ₀²[Pd(RaaiR′)Cl₂]: first-order in Pd(RaaiR′)Cl₂ and second-order in A. The rate increases as follows: Pd(RaaiEt)Cl₂(1) < Pd(RaaiBz)Cl₂(2) and Pd(MeaaiR′)Cl₂(b) < Pd(HaaiR′)Cl₂(a) < Pd(ClaaiR′)Cl₂(c). External addition of Cl⁻ (LiCl) suppresses the rate (rate 1/[Cl⁻]). The activation parameters, H⁰ and S⁰ of the reactions were calculated from the Eyring plot and support the proposed mechanism.     

Manganese(II) complexes of hydrazone based NNO-donor ligands and their catalytic activity in the oxidation of olefins

The reaction between tridentate NNO donor hydrazone ligands, (E)-2-cyano-N′-(phenyl(pyridin-2-yl)methylene)acetohydrazide (HL¹) and (E)-2-cyano-N′-(1-(pyridin-2-yl)ethylidene)acetohydrazide (HL²), with MnCl₂·4H₂O in methanol resulted in [Mn(HL¹)Cl₂(CH₃OH)] (1) and [Mn(HL²)Cl₂(CH₃OH)] (2). Molecular structures of the complexes were determined by single-crystal X-ray diffraction. All of the investigated compounds were further characterized by elemental analysis, FT-IR, TGA, and UV–Vis spectroscopy. These complexes were used as catalysts for olefin oxidation in the presence of tert-butylhydroperoxide (TBHP) as an oxidant. Under similar experimental conditions with equal manganese loading, the presence of [Mn(HL²)Cl₂(CH₃OH)] (2) resulted in higher conversion than [Mn(HL¹)Cl₂(CH₃OH)] (1).     

Synthesis and Structure of Copper(II) Complexes with Methyl [(Pyrazolo-1-carbothioyl)-amino]propionate Derivatives

Methyl 3-[(3,5-dimethylpyrazole-1-carbothioyl)-amino]propionate (L¹) and the optically active derivative of natural monoterpene (+)-3-carene, (3bS,4aR)-3-[(3,4,4-trimethyl-3b,4,4a,5-tetrahydro-cyclopropa[3,4]cyclopenta[1,2-c]pyrazole-1-carbothioyl)-amino]propionate (L²), are synthesized. The paramagnetic CuL¹Cl₂ (I) and [Cu₂L² ₂Cl₄] (II) complexes are obtained. According to the X-ray diffraction data, in mononuclear complex I, the L¹ molecule performs a bidentate-cyclic function due to the coordination of the S atom of the C=S group and the N atom of the pyrazole cycle. The CuCl₂NS coordination polyhedron is a distorted tetrahedron. Two molecules of complex I form an associate due to weak Cu···S interactions. Compound II is binuclear due to the bridging function of two Cl^- ions, and analogous functions of the L¹ and L² ligands. The coordination polyhedron in complex II is CuCl₃NS. The _eff values for compounds I and II are equal to 1.81 and 1.79 _B, respectively, and are constant in the interval from 78 to 300 K, indicating that noticeable exchange interactions between unpaired electrons of the Cu²⁺ ions are absent. The EPR spectra of the complexes in the solid phase are examined.     

酰腙类Schiff碱汞(Ⅱ)配合物的合成及晶体结构

合成了Schiff碱配体3-乙酰吡啶缩邻氨基苯甲酰腙(L1)及4-乙酰吡啶缩邻氨基苯甲酰腙(L2),并分别与Hg Cl2进行了配位反应,得到2个配位聚合物{[Hg(L1)Cl2]·CH3OH}n(1)和[Hg(L2)Cl2]n(2),采用1H NMR、FTIR和元素分析等手段对化合物进行了表征,并对配合物的热稳定性进行了考察。通过X射线单晶体衍射技术测定了2个配合物的单晶结构,结构解析表明,配合物1属于三斜晶系,P1空间群,配合物2属于单斜晶系,P21/n空间群。     

Synthesis and Characterization of Some Ru( tmeda ) Complexes Containing Chloride, Hydride, and Vinylidene Ligands

 The polymeric compound [Ru(cod)Cl₂] _x (cod = cyclooctadiene) reacts with 2 equivalents of tmeda (N,N,N′,N′-tetramethylethylenediamine) in refluxing MeOH to afford trans-[Ru(cod)(tmeda)(Cl)(H)] (1), which upon treatment with CHCl₃ is readily converted to the dichloro complex trans-[Ru(cod)(tmeda)Cl₂] (2). When [Ru(cod)Cl₂] _x is reacted with tmeda under an atmosphere of H₂ (3 bar), the bis-tmeda complex trans-[Ru(tmeda)₂Cl₂] (3) is obtained in 80% yield. DFT calculations revealed that 3 is by 52 kJ/mol more stable than the corresponding cis isomer. Attempts to prepare the coordinatively unsaturated complex [Ru(tmeda)₂Cl]⁺ by reacting 1 with TICF₃SO₃ were unsuccessful. According to DFT calculations, however, such a complex should be stable and, interestingly, should adopt a square pyramidal rather than a trigonal bipyramidal structure. If halide abstraction of 3 is performed in the presence of terminal alkynes HC*CR (R*t-Bu, n-Bu), the cationic vinylidene complexes [Ru(tmeda)₂(Cl)(*C*CHR)]⁺ (4a,b) are obtained.     

A new phenylimidorhenium(V) compound containing the 2-[(2-hydroxyethylimino)methyl]phenol Schiff-base ligand: experimental and theoretical aspects

Reaction of equimolar trans-[Re(NPh)(PPh₃)₂Cl₃] with H₂L, a 1?:?1 Schiff-base condensate of salicylaldehyde and ethanolamine, in chloroform gives trans-[Re(NPh)(HL)(PPh₃)Cl₂] (1a) in good yield. 1a has been characterized by C, H, and N microanalyses, FTIR and UV–vis spectra. The X-ray crystal structure of 1a reveals that it is an octahedral trans-Cl,Cl phenylimidorhenium(V) complex. The rhenium center has an ‘N₂OCl₂P’ coordination sphere. 1a crystallizes in the monoclinic space group P2₁/c with a = 11.2391(5), b = 16.4848(7), c = 16.3761(8) Å, V = 3034.0(2) ų and Z = 4. The electrochemical aspects of 1a have been studied. Electrochemical studies of 1a in dichloromethane show a quasi-reversible Re(V) to Re(VI) oxidation at 1.128 V versus Ag/AgCl. This redox potential reasonably matches the calculated redox potential, 1.186 V versus Ag/AgCl. Geometry optimization of the trans-Cl,Cl 1a vis-à-vis its cis analog, cis-Cl,Cl 1b, have been performed at the level of density functional theory (DFT). It is revealed that 1a is more stable than 1b by 21.6 kcal per mole of energy in the gas phase.     

Crystal structures and intermolecular interactions of two copper(II) complexes with an asymmetric diazine ligand

Reactions of asymmetric ligand N-phenylacetyl picoloylhydrazide (HL) and copper(II) acetate/chloride give two complexes CuL₂ (1) and Cu₂Cl₂L₂ (2). The coordination geometries of Cu(II) in 1 and 2 are a severely distorted octahedron and a distorted square pyramid, respectively. The binuclear copper complex 2 contains a centrosymmetric Cu₂(μ-Cl)₂ core. Individual molecules of 1 and 2 further self-assemble through non-covalent intermolecular bonds in the solid state to form extended 2-D polymers. The magnetic properties, IR, EA, and solid-state photoluminescence properties of the title complexes are presented.     

双吡啶酰腙Schiff碱HgⅡ/Cd(Ⅱ)配合物的合成及其对甲醇蒸气的吸附

合成了双吡啶酰腙Schiff碱配体(L),并采用核磁共振氢谱、质谱、红外光谱和元素分析等手段对其结构进行了表征。进一步采用溶剂挥发法合成了2个配合物{[Cd(L)_2Cl_2]·2DMF·6H_2O}n (1)和[Hg(L)Cl_2]n (2)。通过X射线单晶衍射技术测定了配体及2个配合物的单晶结构,并对配合物的热稳定性及其在常温下对甲醇蒸气的吸附进行了考察。实验结果表明,2个配合物均为1D配位聚合物,配合物1对甲醇蒸气有较好的吸附能力。