Chemisorption Synthesis of the Ion-Polymeric Heteronuclear Gold(III)–Bismuth(III) Complex ([Au{S2CN(C3H7)2}2]3[Bi2Cl9])n Based on [Bi2{S2CN(C3H7)2}6]: 13C MAS NMR,Supramolecular Structure,and Thermal Behavior

Russian Journal of Coordination Chemistry - Chemisorption synthesis on the basis of the binuclear compound [Bi2{S2CN(C3H7)2}6] (I) and preparative isolation of the ion-polymeric heteronuclear...     

Synthesis and structures of two uranyl β-diketonate complexes [UO2(DBM)2(DEDPU)] and [UO2(PMBP)2(DEDPU)]

Two new uranyl β-diketonate complexes [UO₂(DBM)₂(DEDPU)] (1) and [UO₂(PMBP)₂(DEDPU)](CH₃C₆H₅)_0.5 (2), (HDBM?=?dibenzoylmethane, HPMBP?=?1-phenyl-3-methyl-4-benzoyl-5-pyrazolone, DEDPU?=?N,N′-diethyl-N,N′-diphenylurea) were synthesized and characterized. The coordination geometries of the uranyl atoms in 1 and 2 are distorted pentagonal bipyramidal, coordinated by one oxygen atom of DBDPU molecule and four oxygen atoms of two chelating DBM molecules in 1 and PMBP molecules in 2.     

Double Pseudo-Polymeric Gold(III)-Mercury(II) Complexes [Au(S2CNR2)2]nX [R2 = (CH2)6, (CH2)4O] Containing ([HgCl3]−)n, [HgCl4]2− and [Hg2Cl6]2− Anions: Chemisorption Synthesis,Principles of Supramolecular Self-Assembly,and Thermal Behavior

Russian Journal of General Chemistry - Novel pseudo-polymeric complexes of gold(III)-mercury(II) with cyclic alkylene dithiocarbamate ligands: ([Au{S2CN(CH2)6}2][HgCl3])n,...     

Synthesis,crystal structure and luminescent properties of two complexes containing [Au(CN)2] − building blocks

Two supramolecular complexes, {{Ni(H₂O)(phen)₂[Au(CN)₂]}[Au(CN)₂]?·?1.5H₂O} _n (1) (phen?=?1,10-phenanthroline) and [H₂teta][Au₂(CN)₄]?·?2H₂O (2) (teta?=?5,7,7,12,14,14-hexamethyl-1,4,8,11-tetra-azacyocloteradeca-4,11-diene) have been synthesized and structurally characterized. Complex 1 was a one-dimensional infinite chain constructed by [Au(CN)₂]^? building blocks. In complex 2, there are one cation, one anion, and two water molecules in the asymmetric unit. The two complexes are interconnected through a combination of aurophilic attractions and hydrogen bonds and formed into 3D supramolecular structures. The aqueous solutions of 1 and 2 display interesting luminescence at room temperature.     

Synthesis and structures of two cobalt complexes [NaCoII(NTA)(H2O)] n and NH4[CoIII(IDA)2] · 2H2O

Two cobalt complexes [NaCo^II(nta)(H₂O)] _n (H₃nta?=?nitrilotriacetic acid) (1) and NH₄[Co^III(ida)₂]?·?2H₂O (H₂ida?=?iminodiacetic acid) (2) have been synthesized and characterized by single-crystal X-ray diffraction analysis. Compound 1 crystallizes in the orthorhombic system, space group P2₁2₁2₁ with a?=?7.9770(12)?Å, b?=?9.7613(15)?Å, c?=?12.1945(18)?Å, V?=?949.5(2)?ų, Z?=?4, and R ₁?=?0.0705 for 1597 observed reflections. Compound 2 crystallizes in the monoclinic system, space group P2(1)/c with a?=?5.1801(3)?Å, b?=?11.2073(6)?Å, c?=?12.2891(7)?Å, V?=?707.09(7)?ų, Z?=?2, and R ₁?=?0.0349 for 1143 observed reflections. In compound 1, the Co is coordinated by a nitrogen and five oxygen atoms in a distorted octahedral geometry {CoNO₅}, and the Na is coordinated by one water molecule and four carboxyl oxygen atoms in slightly distorted square pyramidal geometry. The entire structure shows a three-dimensional network. In compound 2, Co atom is equatorially coordinated by two ida ligands in a distorted octahedral geometry {CoN₂O₄}. The discrete [Co(ida)₂]^2? anions are linked by hydrogen bonding to a three-dimensional supramolecular network.     

The unusual stability of [NpO2Cl4]2−: Synthesis and characterisation of [NpO2(DPPMO2)2Cl]2[NpO2Cl4] and [Ph3PNH2]2[NpO2Cl4]

The [NpO₂(DPPMO₂)₂Cl][NpO₂Cl₄] complex (where DPPMO₂ = bis(diphenylphosphino)methanedioxide) contains the linear neptunyl group, {NpO₂}²⁺, with two bidentate P=O donor ligands. Coordinating anion Cl^? fills the fifth equatorial coordination site yielding a complex of general formula [NpO₂(DPPMO₂)₂X]₂[Y] (1) (where X = Cl^? and Y = [NpO₂Cl₄]^2?. Reaction between our newly prepared neptunium starting material [NpO₂Cl₂(thf)]_n and phosphinimine ligand produced crystals of [Ph₃PNH₂]₂[NpO₂Cl₄] (2). Compounds 1 and 2 have been structurally characterised.     

Synthesis and structure of bismuth complexes [Ph3MeP] 2 + [BiI3.5Br1.5(C5H5N)]2− · C5H5N, [Ph4Bi] 4 + [Bi4I16]4− · 2Me2C=O, and [Ph3(iso-Am)P] 4 + [Bi8I28]4− · 2Me2C=O

Complexes [Ph₃MeP] ₂ ⁺ [BiI_3.5Br_1.5(C₅H₅N)]^2? · C₅H₅N(I), [Ph₄Bi] ₄ ⁺ [Bi₄I₁₆]^4? · 2Me₂C=O (II), and [Ph₃(iso-Am)P] ₄ ⁺ [Bi₈I₂₈]^4? · 2Me₂C=O (III) were synthesized by reactions of bismuth iodide with triphenylmethylphosphonium bromide, triphenylbismuthonium sulfosalicylate, and triphenylisoamylphosphonium iodide, respectively. The crystal structures of complexes I–III were determined by X-ray crystallography. The complexes contain, in addition to cations and solvent molecules, mono-, tetra-, and octanuclear anions, in which bismuth atoms are in octahedral coordination.     

Syntheses,structures and properties of two complexes bridged by [M(CN)2] − (M = Ag (I), Au (I))

A dinuclear complex Cu₂(bpca)₂(H₂O)₂(Ag₂(CN)₃) (1) and a 1D complex [Cu₂(bpca)₂(H₂O)₂(Au(CN)₂)₂] _n (2) (bpca = bis(2-pyridylcarbonyl)amide anion) have been prepared, structurally characterized and 2 has been magnetically characterized. The magnetic properties show an antiferromagnetic interaction between the two Cu(II) ions. Based on the Hamiltonian ? = ?2J Σ (S_i · S_{i +1}), best fitting for the experimental data leads to J = ?0.045 cm^?1.     

Dimeric and polymeric copper(I) complexes. Synthesis and characterization of copper(I) complexes of di-2-pyridyl ketone oxime (DPKox) and crystal structures of [Cu(DPKox)Cl]2·2H2O and [Cu(DPKox)(NCS)]n

Copper(I) complexes with di-2-pyridylketone oxime (DPKox) of the type CuLX·nH₂O, n=1 for X=Cl and Br, and n=0 for X=I and SCN, have been synthesized and characterized. The overall physical results suggest tridentate and bidentate DPKox ligand in the Cl, Br and I, SCN complexes, respectively, and terminal X in the former but bridging X in the later. These complexes display MLCT bands in the visible region, but they do not fluoresce at room temperature. The structure determination has shown the chloride complex (1) to have a centro-symmetrically related dimeric unit, in which each copper atom is coordinated by Cl(1), N(1), N(2) and N(3) (of the second ligand molecule) in a distorted tetrahedral environment. Hydrogen bonds are formed by the O(1) of the oxime group and a lattice water molecule, and between different lattice water molecules and Cl(1). The structure of the thiocyanate complex (2) features tetrahedral geometry around copper atoms, a chelating bidentate DPKox ligand coordinating via one of the two pyridyl nitrogens, N(1), and N(oxime) only and μ-1,3-thiocyanate group forming zigzag chains along the c-axis of the unit cell.     

Gold(III) preconcentration from acid solutions by cadmium diisopropyldithiocarbamate: Gold(III)-binding species, supramolecular structure, and thermal properties of the heteropolynuclear complex ([Au{S2CN(iso-C3H7)2}2]2[CdCl4] · 1/2C3H6O) n

The reaction of binuclear cadmium diisopropyldithiocarbamate with a solution of AuCl₃ in 2 M HCl was studied. The heterogeneous reaction of gold(III) binding follows a chemisorption scenario (in combination with partial ion exchange) and yields a heteropolynuclear gold(III)-cadmium complex. The molecular and crystal structure of a solvated species of the compound, namely ([Au{S₂CN(iso-C₃H₇)₂}₂]₂[CdCl₄] · 1/2C₃H₆O) _n (I), was solved by X-ray crystallography. The structure of complex I contains (in the ratio 1: 1) structurally nonequivalent molecular cations [Au{S₂CN(iso-C₃H₇)₂}₂]⁺; the differences between these cations allow them to be classified as conformational isomers (cations A and B). The specifics of the supramolecular organization of complex I consist of the alternation of layers of [Au₂{S₂CN(iso-C₃H₇)₂}₄]²⁺ binuclear cations (formed by cations A), ([Au{S₂CN(iso-C₃H₇)₂}₂]⁺) _n polymer chains (formed by cations B), and [CdCl₄]^2? anions. The chemisorption capacity of the precursor cadmium diisopropyldithiocarbamate as calculated from the gold(III) binding reaction is 423.5 mg Au³⁺ per gram of sorbent. The thermal properties of complex I were studied by simultaneous thermal analysis (STA) in order for the parameters of sorbed gold recovery to be determined. The multistep thermal destruction process involves desorption of solvating acetone molecules, thermolysis of the dithiocarbamate part of the complex and [CdCl₄]^2? with release of metallic gold and cadmium chloride and formation of CdS, as well as vaporization of CdCl₂ and CdS. The only final product of thermal conversions is reduced metallic gold.     

Cyanide-bridged bi- and trinuclear heterobimetallic Fe(III)–Mn(III) complexes: Synthesis,crystal structures and magnetic properties

By employing trans-dicyano or pentacyanometalate as building block and using a bicompartimental Schiffbase based manganese(III) compound as assemble segment, two new cyanide-bridged heterometallic Fe(III)–Mn(III) complexes {[Mn(L)(H₂O)][Febpb(CN)₂]}·2CH₃OH (1) and {[Mn(L)(H₂O)]₂··[Fe(CN)₅NO]} (2) (bpb^2– = 1,2-bis(pyridine-2-carboxamido)benzenate, L = N,N'-ethylene-bis(3-ethoxysalicylideneiminate) have been synthesized and characterized by elemental analysis, IR spectroscopy and X-ray structure determination. Single X-ray diffraction analysis reveals binuclear FeMn and trinuclear FeMn₂ structure, respectively, in which the cyanide precursor acts as mono- or bidentate ligand to connect the Mn(III) Schiff-base unit(s). Furthermore, these two complexes are self-complementary through coordinated aqua ligands from one complex and the free O₄ compartments from the neighboring complex, giving dimeric and 1D single chain supramolecular structure. Investigation of the magnetic susceptibility of 1 reveals weak antiferromagnetic coupling between the adjacent Mn(III) ions. Based on the binuclear FeMn model, best fit of the magnetic susceptibilities of 1 leads to the magnetic coupling constants J =–1.37 cm^–1 and zJ′ =–0.72 cm^–1 (1).     

Synthesis,spectroscopic, and biological activities of two binuclear complexes [Cu(II)(1-phenylamidino-O-methylurea)2(H2O)]2(Cl2)2 and [Cu(II)(1-phenylamidino-O-i-butylurea)tmen]2(Cl2)2·2H2O

EPR spectra of two copper(II) binuclear complexes, [Cu(II)(1-phenylamidino-O-methylurea)₂(H₂O)]₂(Cl₂)₂ (1) and [Cu(II)(1-phenylamidino-O-i-butylurea)tmen]₂(Cl₂)₂?·?2H₂O (2), at room temperature showed fine structure transitions (ΔM _s?=?±1) and a very weak half-field signal corresponding to forbidden transitions (ΔM _s?=?±2). The spectrum of 1 showed disappearance of normal and half-field transitions when cooled to 77?K, suggesting antiferromagnetical coupling dicopper complex which is also supported by the low magnetic moments (µ _eff?=?1.64?B.M.). The isotropic exchange interaction constant J (41?cm^?1) for 2 indicated that interaction between the two spins of the binuclear complex is ferromagnetic, confirmed from the high magnetic moment value (µ _eff?=?2.25?B.M.). The binding of these complexes with calf thymus DNA suggested that these complexes interact with DNA by electrostatic or groove binding, not by intercalation. The two complexes have good antibacterial activity against tested bacteria responsible for urinary tract infection.     

Synthesis,crystal structure and magnetic properties of A[Ni(mnt)2] complexes [A = 1-(4-nitrobenzyl)quinolinium or 1-benzylpyridinium; mnt2− = maleonitriledithiolate]

Two new ion-pair complexes A[Ni(mnt)₂], [A = 1-(4-nitrobenzyl)quinolinium (1), and 1-benzylpyridinium (2)] have been prepared and characterized. The crystal structure of (1) has been determined by X-ray diffraction analysis. In the solid state, anions and cations of (1) form completely segregated stacking columns, with the Ni···Ni distances alternating between 3.890(4) and 4.965(5) Å in the [Ni(mnt)₂]^– stacking column. The variable temperature magnetic susceptibilities of (1) and (2) have been measured over the 77–300 K range and the results reveal that (1) is diamagnetic and that (2) shows a weak antiferromagnetic spin exchange interaction between the metal ions. The e.p.r. spectra of (1) and (2) in MeCN at room temperature were similar, the g-values being almost identical.     

Chemisorption of the [AuCl4]− anion by cadmium cyclo-pentamethylenedithiocarbamate and the resulting bound-gold(III) species: The supramolecular structure and thermal behavior of the polynuclear complexes ([Au{S2CN(CH2)5}2]2[CdCl4]) n and ([Au{S2CN(CH2)5}Cl2]) n

The interaction between cadmium cyclo-pentamethylenedithiocarbamate (chemisorbent Ia) and the [AuCl₄]^? anion in 2 M HCl has been investigated. The state of the chemisorbent in contact with AuCl₃ solutions has been probed by ¹¹³Cd MAS NMR spectroscopy. The heterogeneous reactions in the system, including gold(III) chemisorption from the solution and partial ion exchange, yield the gold(III)-cadmium heteropolynuclear complex ([Au{S₂CN(CH₂)₅}₂]₂[CdCl₄]) _n (I) and the polynuclear mixed-ligand complex ([Au{S₂CN(CH₂)₅}Cl₂]) _n (II). The crystal and molecular structures of these compounds have been determined by X-ray crystallography. The main structural units of the compounds are the complex cation [Au{S₂CN(CH₂)₅}₂]⁺, [CdCl₄]^2? anion (in I), and Au{S₂CN(CH₂)₅}Cl₂ molecule (in II). The further structural self-organization of the complexes at the supramolecular level is due to secondary Au...S and Au...Au bonds. [Au₂{S₂CN(CH₂)₅}₄]²⁺ dinuclear cations form in the structure of I, which then polymerize into ([Au₂{S₂CN(CH₂)₅}₄]²⁺) _n chains. In the structure of II, adjacent Au{S₂CN(CH₂)₅}Cl₂ molecules join by forming pairs of asymmetric secondary Au...S bonds, producing polymer chains with alternating antiparallel monomer units. The chemisorption capacity values calculated for cadmium cyclo-pentamethylenedithiocarbamate from gold(III) binding reactions are 455 and 910 mg of gold per gram of sorbent. The gold recovery conditions have been determined by investigating the thermal behavior of I and II by synchronous thermal analysis. The multistep thermal destruction of ionic complex I includes the thermolysis of its carbamate moiety and [CdCl₄]_2? (which liberates gold metal and cadmium chloride and yield some amount of CdS) and CdCl₂ and CdS evaporation. The thermolysis of II proceeds via the formation of Au₂S and AuCl as intermediate compounds. In both cases, the ultimate pyrolysis product is elemental gold.     

Carbonate complexes [C(NH2)3]6[An(CO3)5] · nH2O (An = Th, U, Np, and Pu; n = 3 and 4): Synthesis and structures

Two series of isostructural double An(IV) and guanidinium carbonates were obtained as single crystals of the formula [C(NH₂)₃]₆[An(CO₃)₅] · nH₂O (An = Th, U, Np, and Pu; n = 3 (I) and 4 (II)) and examined by X-ray diffraction. For the Pu(IV) complexes, a = 10.490(2) Å, b = 33.798(5) Å, c = 10.519(2) Å, β = 119.414(7)°, space group P2₁/c, Z = 4, R = 0.0369 (I) and a = 16.0895(18) Å, b = 13.1458(14) Å, c = 16.6951(18) Å, β = 108.116(6)°, space group C2/c, Z = 4, R = 0.0171 (II). Both series of complexes contain the anions [An(CO₃)₅]^6?, in which the An atom is coordinated to five chelating bidenate carbonate ions. The coordination polyhedra of the An atoms are distorted bicapped square antiprisms. Within both the series, the An-O bond lengths decrease monotonically only for the sequence Th-U-Np. The average Np-O and Pu-O bond lengths in both tri- and tetrahydrates are virtually equal. The IR and electronic absorption spectra of the complexes obtained were studied. The absorption bands due to the f-f transitions experience bathochromic shifts in the spectra of the U⁴⁺ and Pu⁴⁺ carbonate complexes and hypsochromic shifts in the spectra of the Np⁴⁺ complexes.     

Synthesis and structures of mercury and cadmium complexes: [Ph4Sb] 2 + [Hg2I6]2−·Ph2Hg, [Ph4Sb] 2 + [E2I6]2− (E = Hg, Cd), and [Ph4Sb] 2 + [Hg4I10]2−

The reaction of pentaphenylantimony with mercury iodide affords the ionic complex [Ph₄Sb] ₂ ⁺ [Hg₂I₆]^2?·Ph₂Hg (I). The [Ph₄Sb] ₂ ⁺ [Hg₂I₆]^2? (II) and [Ph₄Sb] ₂ ⁺ [Cd₂I₆]^2? (III) complexes are synthesized from tetraphenylantimony iodide and mercury and cadmium iodides. The [Ph₄Sb] ₂ ⁺ [Hg₄I₁₀]^2? complex (IV) is prepared from tetraphenylantimony 2,4-dimethylbenzenesulfonate and mercury iodide. According to the X-ray diffraction data, the Sb atom in the [Ph₄Sb]⁺ cations of complex I has virtually ideal tetrahedral coordination (the CSbC angles are 108.09°–109.64°). In the central square fragment Hg₂I₂ of the [Hg₂I₆]^2? anion, the Hg-I_br bond lengths are 2.825 and 3.075 Å, and the terminal iodine atoms are more strongly bonded to the mercury atoms (Hg-I_term 2.691 and 2.700 Å). The [Cd₂I₆]^2? anion in complex III has a similar structure (the Cd-I_bridg and Cd-I_term distances are 2.865, 2.872 and 2.723, 2.748 Å, respectively). The anions in complex IV are joined by I…Hg (3.651 Å) and I…I (4.058 Å) interactions into an infinite dimeric network.     

Synthesis,Structure and Luminescent Properties of [Zn(btzb)2Cl2]·2H2O[btzb=1,2-Bis(5-tetrazolyl)benzene]

The title compound[Zn(btzb)2Cl2]·2H2O(1·2H2O,btzb=1,2-bis(5-tetrazolyl)benzene)was synthesized in situ by the[2 3] cycloaddition reaction of phthalonitrile with NaN3 in water in the presence of ZnCl2 under refluxing conditions.1·2H2O crystallizes in the monoclinic system,space group P21/c with a=9.0119(18),b=7.5566(15),c=18.076(5)(A),β=114.67(2)°,V=1118.6(4)(A)3,Z=2,Dc=1.784 g/cm3 T=223(2)K,C16H16N16O2Cl2Zn,Mr=600.74,F(000)=608,μ(MoKα)=1.393 mm-1,S=1.081,R=0.0306 and wR=0.0669 for 1896 observed reflections with Ⅰ ＞2σ(Ⅰ).The Zn2 ion of 1 is coordinated by four N atoms from two btzb ligands and two Cl atoms,forming a distorted octahedral coordination geometry.A number of intermolecular hydrogen bonding interactions between molecules 1 and/or the solvated water molecules result in a 3D hydrogen-bonded structure.The luminescent property of 1·2H2O was also investigated.     

Synthesis and crystal structures of dialkyl[1,1-bis(alkylchloroalanyl)organylmethyl]phosphine•dialkylchloroalane(1/1) complexes

Dialkyl[1,1-bis(alkylchloroalanyl)organylmethyl]phosphine?dialkylchloroalane(1/1) complexes (1a–1d) were synthesized and fully characterized. In 1a–1d, dative bonding between phosphorus or chlorine as a donor atom and aluminum as an acceptor atom results in a bicyclic system. The ³¹P{¹H} NMR spectra of all compounds dissolved in d₆-benzene indicate the presence of several isomers in solution. The ²⁷Al{¹H} NMR spectra of 1a–1d dissolved in d₆-benzene as well show very broad singlets between 177 and 140 ppm. For all compounds, crystal structures consist of two fused four- and five-membered rings. The 1λ³-phosphaalkyne reacts at the Al–C bond of the starting material, whereas the Al–Cl moiety remains intact. The heterocycle isolated is a molecular complex of the underlying insertion compound and a third equivalent of dialkylaluminum chloride. The four- and five-membered rings both contain two chlorine-bridged aluminum atoms, Al3 and Al1, slightly more symmetrical than that between Al1 and Al6. In the four-membered ring the two aluminum atoms Al1 and Al6 approach each other at an average distance of 289.1 pm which tallies with the element–element distance (286.3 pm) in aluminum metal.