3,6-Di-tert-butyl-o-benzosemiquinone complexes of copper(1) with bidentate bis(diphenylphosphine) ligands. Synthesis, structures, and properties

New mononuclear 3,6-di-tert-butyl-o-benzosemiquinone complexes of copper(1) with bis(diphenylphosphine) ligands were synthesized: (DBSQ)Cu(dppe) (1) (DBSQ=3,6-di-tert-butyl-o-benzosemiquinone and dppe=1,2-bis(diphenylphosphino)ethane), (DBSQ)Cu(dppp) (2) (dppp=1,3-bis(diphenylphosphino)propane), (DBSQ)Cu(dppn) (3) (dppn=2,2′-bis(diphenylphosphino)-1,1′-binaphthyl), and (DBSQ)Cu(dppfc) (4) (dppfc=1,1′-bis(diphenylphosphino)ferrocene). The compositions and structures of complexes1–4 were characterized by elemental analysis and electronic absorption, IR, and ESR spectroscopy. The molecular structures of complexes3 and4 were established by X-ray diffraction analysis. The reactions of elimination and replacement of neutral ligands in the coordination sphere of the complexes were studied by ESR spectroscopy. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2333–2340, November, 1998.     

catena‐Poly[[bis(nicotinamide‐κN1)copper(I)]‐μ‐thiocyanato‐κ2N:S]

The Cu^I cations in the title compound, [Cu(NCS)(C₆H₆N₂O)₂]_n, are coordinated by N atoms from each of two mirror‐related nicotin­amide ligands, as well as by one N atom of one thio­cyanate ligand and one S atom of a symmetry‐related thio­cyanate ligand, within a slightly distorted tetrahedron. The Cu^I cations and the thio­cyanate anions are located on a crystallographic mirror plane and the nicotin­amide ligands occupy general positions. The Cu^I cations are connected by the thio­cyanate anions to form chains in the direction of the crystallographic a axis. These chains are connected by hydrogen bonds between the amide H atoms and the O atoms of adjacent nicotin­amide ligands, to give a three‐dimensional structure.     

Two manganese(II) coordination polymers containing semirigid bis(benzimidazole) ligands: synthesis,crystal structures,and catalytic properties

Two ternary mixed Mn(II) coordination polymers (CPs), namely [Mn(L1)(Hnip)₂] _n (1) and [Mn(H_0.5L2)₂(H_1.5btc)₂] _n (2) (H₂nip = 5-nitroisophthalic acid, L1 = 1, 4-bis(5,6-dimethylbenzimidazol-1-ylmethyl)benzene, H₃btc = 1,3,5-benzenetricarboxylic acid, L2 = 4,4′-bis(benzimidazol-1-ylmethyl)biphenyl), have been synthesized under hydrothermal conditions and structurally characterized. CP 1 exhibits a non-interpenetrated six-connected pcu framework with the point symbol {4¹²·6³}, while CP 2 features a metal-carboxylate loop-like chain, which is further assembled into a 3D supramolecular network via hydrogen bonds and π–π interactions. The thermal stabilities, luminescence, and catalytic properties of both CPs for the degradation of methyl orange in a Fenton-like reaction have also been investigated.     

A new family of pyrazolyl-based anionic bidentate ligands and crystal structure of bis(N-phenyl-2-pyrazolyl-1-carboximidothioato)copper(II)

Three new N,S-donor bidentate pyrazolyl-based ligands abbreviated as [PhNCSPz]⁻, 1, [PhNCSPz^Me2]⁻, 2, and [PhNCSPz^Ph2]⁻, 3, have been synthesized in THF by direct mixing of phenylisothiocyanide with suspension of appropriate sodium-pyrazolate salts and characterized by the common spectroscopic and analytical methods. The Cu(II) complexes of these anionic chelate ligands have been characterized and the crystal structure of Cu(PhNCSPz)₂, 4, has been determined. The space group of complex is P2₁c, with a = 5.9313(3), b = 21.206(1) Å, c = 8.0667(4) Å, β = 103.822(1)°.     

Synthesis,crystal structures,and thermal and thermodynamic properties of dimorphic copper(I) coordination polymers

A second modification of the literature-known copper(I) coordination polymer CuCl(pyridazine) was prepared by the reaction of CuCl with pyridazine in acetonitrile. The crystal structure of catena[CuCl(mu(2)-pyridazine-N,N)] is built up of CuCl chains of which each two are connected by the pyridazine ligands to form double chains that are directed parallel to the crystallographic a-axis. In the literature known form LI (CuCl)(2) dimers occur that are connected to chains by the pyridazine ligand. On heating, compound I and LI lose half of the pyridazine ligands and transform to the new 2:1 coordination polymer poly[(CuCl)(2)(pyridazine-N,N)] (II), which transforms at higher temperatures to CuCl. The crystal structure of II is composed of discrete CuCl tetra-chains that are linked by the pyridazine ligands to sheets parallel to (010). The same thermal reactivity is found for the literature-known compound CuBr(pyridazine) (LII), which is isotypic to LI. On heating LII a transformation into the new 2:1 compound poly[(CuBr)(2)(pyridazine-N,N)] (III) is observed, which is isotypic to II. The thermal reactivity of all compounds and the transformation behavior as well as the range of thermodynamic stability of the dimorphic modifications were studied using DTA-TG-MS and DSC measurements, temperature dependent X-ray powder investigations, and crystallization experiments.     

Synthesis,crystal structure and photo-induced isomerization of [ N,N ′- bis (4-fluorobenzylidene) ethylenediamine]bromo(triphenylphosphine)copper(I) complex

Abstract

The electrochemical behavior of VOQ₂OH or [VOQ₂-OVOQ₂] (Q = 8-hydroxyquinohnate anion) has been investigated by cyclic voltammetry in acetonitnie solutions. Although both species exist simultaneously at every condition analyzed, they can be clearly differentiated by this method. The effect of trace amounts of water on the electrochemical behavior is also discussed.     

A novel azide copper complex: [[Azido{bis[2-(piperidin-1-ylmethyl)pyridine]}copper(II)]perchlorate] hydrate

Synthesis and single crystal X-ray diffraction study were carried for compound {[Cu(C₁₁H₁₆N₄)₂(N₃)](ClO₄)} · H₂O (I). The structure is molecular, and the Cu²⁺ ion is in a five-coordinated compressed trigonal bipyramid environment. Copper ion is bound to five N atoms, in which four N atoms are from two chlelating ligands 2-(piperidin-1-ylmethyl)pyridine and the fifth N donor is from a monodentate azido ligand. The complex cations [Cu(C₁₁H₁₆N₄)₂(N₃)]⁺, the perchlorate anions, and solvent water molecules are further joined into three dimensional supramolecular networks by rich hydrogen bonds including strong O-H…N between solvent water and azide ion and O-H…O between solvent water and perchlorate ion, and weak hydrogen bonds C-H…O, and weak bifurcated hydrogen bonds C-H/C-H…N in which N atom of azide ion serving as bifurcated acceptor and two C-H groups as donors.     

Syntheses,crystal structures and properties of two cadmium coordination polymers containing bis (2-methylimidazol-1-yl)methane(2-mBIM) and bis (imidazol-1-yl)methane (BIM) ligands

Coordination polymers, {[Cd(2-mBIM)₃](ClO₄)₂} _n (1) and [Cd(BIM)₂(NO₃)₂] _n (2), have been prepared from the reaction of bis(2-methylimidazol-1-yl)methane(2-mBIM) with Cd(ClO₄)₂ and bis(imidazol-1-yl)methane (BIM) with Cd(NO₃)₂ in ethanol and water, respectively. Their structures were characterized by single crystal X-ray diffraction and IR spectroscopy. Compound 1 crystallizes in the rhombohedral space group R-3c with a = b = 12.3617(5) Å, c = 38.896(3) Å, γ = 120°, V = 5147.5(5) ų, z = 6. The Cd^II occupies a crystallographic inversion center and is coordinated by six N atoms from six distinct 2-mBIM ligands to form a slightly distorted octahedral geometry. Each 2-mBIM is coordinated to two Cd^II cations, linking alternatively four Cd^II cations, resulting in a 32-membered M₄L₄ macrometallacycle. Compound 2 crystallizes in the monoclinic space group C2/m with a = 14.400(3) Å, b = 9.3894(18) Å, c = 8.6926(17) Å, β = 123.499(2)°, V = 980.1(3) ų, z = 2. The Cd coordinates to four nitrogen atoms from four different BIM and two nitrates to form a slightly distorted octahedral geometry. The BIM ligands bridge to form a 1-D infinite double-bridged chain structure with 16-membered M₂L₂ macrometallacyclic structural units.