Inorganic Chemistry Communications (v.9, #12)

Contents List (iii-xiv).

The trans-configurated square-planar palladium complex trans-[{(Ph2PC6H4CONH)2C6H4}PdCl2] (1), which catalyzes the Suzuki cross copuling of 4-bromotoluene with phenylboronic acid, was found to react with potassium carbonate in toluene at 90 °C (Suzuki conditions) to give cis-[{(Ph2PC6H4CON)2C6H4}Pd] (2). Both complexes 1 and 2 show approximately the same catalytic performance for Suzuki reactions, suggesting 2 to be the catalytically active species.The trans-configurated square-planar palladium complex trans-[{(Ph2PC6H4CONH)2C6H4}PdCl2] (1), which catalyzes the Suzuki cross coupling of 4-bromotoluene with phenylboronic acid, was found to react with potassium carbonate in toluene at 90 °C (Suzuki conditions) to give cis-[{(Ph2PC6H4CON)2C6H4}Pd] (2). The single-crystal X-ray structure analysis of 2 reveals the square-planar palladium center to be in a cis configuration. The trans–cis configuration change at palladium is possible because of the elimination of two HCl equivalents in the conversion of 1 into 2. Both complexes 1 and 2 show approximately the same catalytic performance for Suzuki reactions, suggesting 2 to be the catalytically active species.
Keywords: Palladium complexes; Suzuki cross-coupling; Square-planar geometry; cis and trans configuration;

The X-ray crystal structures of 1 [2[AMPYH] · [(Cu (H2O) (mal)2)]:2H2O] and 2 [2[AMPYH] · [ZnBr (Hmal) (mal)]:2H2O ] [mal = malonate; Hmal = hydrogen malonate; AMPYH = 2-amino-4,6-dimethylpyrimidinium] reveal the interplay of metal-coordination motifs and the hydrogen-bonding patterns. In both the structures, the 2-amino-4,6-dimethylpyrimidine cations are not directly coordinated to copper and zinc, but are hydrogen-bonded to the malonate ion. The protonated endocyclic nitrogen and the amino group of 2-amino-4,6-dimethylpyrimidine molecule interact with malonate ligand via a pair of N–H⋯O hydrogen-bonds, (with graph set notation R 2 2 ( 8 ) ) whereas the unprotonated endocyclic nitrogen and the amino group interact with the malonate ligand via N–H..O and C–H⋯N hydrogen-bonds forming the same R 2 2 ( 8 ) motif. The combination of hydrogen-bonding motif and metal-coordination motif creates a novel supramolecular motif. The interplay of the hydrogen-bonding motif and metal-coordination motif via hydrogen bonds leads to similar supramolecular motifs in both the structures.The X-ray crystal structures of 1 [2[AMPYH] · [(Cu (H2O) (mal)2)]:2H2O] and 2 [2[AMPYH] · [ZnBr (Hmal) (mal)]:2H2O ] [mal = malonate; Hmal = hydrogen malonate; AMPYH = 2-amino-4, 6-dimethylpyrimidinium] reveal the interplay of metal-coordination motifs and the hydrogen-bonding patterns . In both the structures, the 2-amino-4,6-dimethylpyrimidine cations are not directly coordinated to copper and zinc, but are hydrogen-bonded to the malonate ion. The protonated endocyclic nitrogen and the amino group of 2-amino-4,6-dimethylpyrimidine molecule interact with malonate ligand via a pair of N–H⋯O hydrogen-bonds, (with graph set notation R 2 2 ( 8 ) ) whereas the unprotonated endocyclic nitrogen and the amino group interact with the malonate ligand via N–H..O and C–H⋯N hydrogen-bonds forming the same R 2 2 ( 8 ) motif. The combination of hydrogen-bonding motif and metal-coordination motif creates a novel supramolecular motif. The interplay of the hydrogen-bonding motif and metal-coordination motif via hydrogen-bonds leads to similar supramolecular motifs in both the structures.
Keywords: Hydrogen-bonding motif; Metal-coordination motif; Hydrogen-bonded duplex; Carboxyl–carboxylate interactions;

Reaction of AgNO3 and 1,3-thiazolidine-2-thione (tzdtH) in chloroform at low temperatures yielded a 3D [Ag4(tzdt)4(μ- tzdtH)2] n network which exhibiting a strong silver-silver interaction(2.9002 Å). In the open framework, two helical chains along two directions is observed.A novel metal-organic framework (MOF), the first 3D 1,3-thiazolidine-2-thione (tzdtH) coordinated MOF with strong Ag–Ag interaction (2.9001 Å) in tetranuclear silver clusters, was synthesized. The single-crystal X-ray diffraction shows that the versatile ligand tzdtH contributes greatly to the formation of the 3D framework and the helical structure.
Keywords: 1,3-Thiazolidine-2-thione; Single-crystal X-ray diffraction; Strong Ag–Ag interaction; Helical structure;

[Mn(phen){3,5-(NO2)2sal2−}] n is a one-dimensional helical structure with Mn atoms in five coordination environment. La2(phen)3{3,5-(NO2)2sal2−}2(NO3)(OH) is a tetranuclear lanthanum complex.The hydrothermal reaction of manganese chloride and lanthanum nitrate with 3,5-dinitrosalicylic acid (3,5-(NO2)2sal) and 1,10-phenanthroline (phen) yielded two compounds [Mn(phen){3,5-(NO2)2sal2−}] n (1) and La2(phen)3{3,5-(NO2)2sal2−}2 (NO3)(OH) (2). Magnetic susceptibility measurements show weak antiferromagnetic interactions in (1).
Keywords: Coordination polymers; Hydrothermal synthesis; 3,5-Dinitrosalicylic acid ligand;

Self-assembly of neutral dinuclear and trinuclear zinc-benzoate complexes by Anirban Karmakar; Rupam J. Sarma; Jubaraj B. Baruah (1169-1172).
A structurally important self-assembly of dinuclear and trinuclear zinc-benzoate complexes having formula [Zn3(μ-OBz)6(py)2] ·  [Zn2(OBz)4(py)2] (A) (where OBz is benzoate and py is pyridine ligand) is reported. The dinuclear and trinuclear complexes present in the crystal lattice of the self-assembly are held together by weak C–H⋯π and C–H⋯O interactions.A structurally important self-assembly of dinuclear and trinuclear zinc-benzoate complexes having formula [Zn3(μ-OBz)6(py)2] · [Zn2(OBz)4(py)2] (A) (where OBz is benzoate and py is pyridine ligand) is reported. The dinuclear and trinuclear complexes present in the crystal lattice of the self-assembly are held together by weak C–H⋯π and C–H⋯O interactions.
Keywords: Zinc benzoate; Polynuclear complex; Self assembly; Crystal structure;

Synthesis, structure and magnetic properties of the first copper(II) complex with an (E)-4-aryl-4-oxo-2-butenoato ligand by Zoran M. Miodragović; Goran A. Bogdanović; Bojana B. Krajčinović; Branko J. Drakulić; Vladan B. Kusigerski; Djenana U. Miodragović; Vojislav V. Spasojević; Ismet M. Hodžić; Ivan O. Juranić (1173-1177).
A new binuclear Cu(II) complex with the (E)-4-(2,4-diisopropylphenyl)-4-oxo-2-butenoato ligand (L) was synthesized. The structures of (E)-4-(2,4-diisopropylphenyl)-4-oxo-2-butenoic acid (HL), and corresponding (tetrakis)-μ-[(E)-4-(2,4-diisopropylphenyl)-4-oxo-2-butenoato]-bis(ethanol)-copper(II) complex, [Cu2L4(C2H5OH)2], are determined by single crystal X-ray analyses. Strong anti-ferromagnetic intradimer coupling with an exchange integral value 2J of −260 cm−1 is established for the isolated complex.A new binuclear Cu(II) complex with an (E)-4-(2,4-diisopropylphenyl)-4-oxo-2-butenoato ligand (L) was successfully synthesized and characterized by elemental analysis and IR-spectroscopy. The structures of (E)-4-(2,4-diisopropylphenyl)-4-oxo-2-butenoic acid (HL), and the corresponding (tetrakis)-μ-[(E)-4-(2,4-diisopropylphenyl)-4-oxo-2-butenoato]-bis(ethanol)-copper(II) complex, [Cu2L4(C2H5OH)2], were determined by single crystal X-ray analyses and are preliminarily discussed. This is the first complex of a transition metal with ligand L, as well as the first determined crystal structure of a metal complex with this type of ligand. Analysis of the magnetic susceptibility measurements of the isolated [Cu2L4(C2H5OH)2] · H2O complex shows the existence of a strong anti-ferromagnetic intradimer coupling, with an exchange integral value 2J of −260 cm−1.
Keywords: (E)-4-(2,4-diisopropylphenyl)-4-oxo-2-butenoato ligand; Cu(II) complexes; X-ray analysis; Magnetic properties;

An unusual dichromium(II,II) compound bearing di-2-pyridyl ketone oximate ligands and prepared by the ligand-assisted reduction of a trichromium(III,III,III) complex in air by Theocharis C. Stamatatos; Konstantina V. Pringouri; Catherine P. Raptopoulou; Ramon Vicente; Vassilis Psycharis; Albert Escuer; Spyros P. Perlepes (1178-1182).
The reaction of a triangular, oxide-centred trichromium(III,III,III) pivalate cluster with di-2-pyridyl ketone oxime ▪ in MeCN under refluxing aerobic conditions has led to a novel, pivalate-free dichromium(II,II) complex via a ligand-assisted reduction of the chromium(III) starting material; the dinuclear molecule contains high-spin, trigonal bipyramidal CrII atoms, and possesses both bridging and terminal oximate ligands.The reaction of the oxide-centred triangular, trichromium(III,III,III) complex [Cr3O(O2CCMe3)6(H2O)3](O2CCMe3) with di-2-pyridyl ketone oxime, (py)2CNOH, in MeCN under aerobic and refluxing conditions yields the pivalate-free, dichromium(II,II) complex [Cr2{(py)2CNO}4] · 2H2O (1  · 2H2O). The dinuclear complex can also be prepared by the reaction of [Cr(CO)6] with (py)2CNOH in refluxing MeCN/H2O in air. The two high-spin CrII atoms are doubly bridged by two 2.1110 oximate ligands, while a chelating 1.0110 (py)2CNO ion completes distorted trigonal bipyramidal coordination at each metal centre. The dimers are stabilized by intramolecular stacking interactions between the terminal (py)2CNO ligands, and the structural effects of these interactions are discussed.
Keywords: Dichromium(II,II) complexes; Di-2-pyridyl ketone oximate complexes; Ligand-assisted reduction of chromium(III); π–π Stacking interactions; Trigonal bipyramidal chromium(II);

Peculiar sandwich-like π–π interaction regulating the nonplanarity of the model heme crystals by Yoshiki Ohgo; Akito Hoshino; Hidehiro Uekusa; Mikio Nakamura (1183-1186).
X-ray crystallographic analysis of bis(pyridine N-oxide) complexes of iron(III) porphyrinates has revealed that the two pyridine rings of the axial ligands correctly sandwich the porphyrin ring to induce the unusual deformation toward commonly observed S4 saddled porphyrin ring.X-ray crystallographic analysis of bis(pyridine N-oxide) complexes of iron(III) porphyrinates has revealed that the two pyridine rings of the axial ligands correctly sandwich the porphyrin ring to induce the deformation of commonly observed S4 saddled porphyrin ring.
Keywords: Deformed porphyrin; Iron(III); Hemeprotein;

Two novel lanthanide (Nd, Gd) coordination polymers with chromate anion as building block of the 2D metal oxide by Jiu-Hui Liu; Xiao-Yuan Wu; Quan-Zheng Zheng; Xiang He; Wen-Bin Yang; Can-Zhong Lu (1187-1190).
Two novel lanthanide coordination polymers, [Nd(IN)CrO4] n (1) and [Gd(IN)CrO4] n (2) (HIN = isonicotinic acid), have been synthesized and characterized. The single-crystal X-ray diffraction studies reveal that 1 and 2 are three-dimensional structures. Magnetic measurements for compounds 1 and 2 both show antiferromagnetic-like interaction properties.Two novel lanthanide coordination polymers, [Nd(IN)CrO4] n (1) and [Gd(IN)CrO4] n (2) (HIN = isonicotinic acid), were obtained from the reaction of Ln2O3, HIN and K2Cr2O7 under hydrothermal conditions. The single-crystal X-ray diffraction studies reveal that 1 and 2 are isostructural. Compounds 1 and 2 are three-dimensional frameworks consisting of inorganic layers of Ln and CrO 4 2 - pillared by the organic IN. Each CrO 4 2 - anion in the structure binds four Nd(III) ions in an η34-pentadentate coordination mode. Measurements of magnetic susceptibilities for Compounds 1 and 2 indicate the presence of antiferromagnetic interactions.
Keywords: Lanthanide coordination polymer; Chromate anion; Layered structure; Zigzag-like arrangement;

A novel hybrid compound [Na(C20H24O6)(CH3CN)2]2[Mo6O19] · 4CH3CN (1) displays three-dimensional hydrogen bonding network consisting of one-dimensional sandglass channels that are filled by guest solvent molecules.A novel supramolecular assembly consisting of sodium-dibenzo-18-crown-6(DB18C6) complex cation [Na(C20H24O6)(CH3CN)2]2+ and isopolyanion [Mo6O19]2− has been demonstrated in the 3D structure of [Na(C20H24O6)(CH3CN)2]2[Mo6O19] · 4CH3CN (1). Weak intermolecular forces (C–H⋯O hydrogen bonds) between isopolyanion and crown ether play a significant role in the construction of supramolecular framework in the crystal structure of 1. Compound 1 has been characterized in the solid state by single crystal X-ray diffraction, IR, CHN analysis, and TGA.
Keywords: Dibenzo-18-crown-6; Supramolecular assembly; Polyoxoanion; ABAB arrangement;

A new, dinuclear high spin manganese(III) complex with bridging phenoxy and methoxy groups. Structure and magnetic properties by Magnus F. Anderlund; J. Zheng; Mårten Ghiladi; Mikael Kritikos; Eric Rivière; Licheng Sun; Jean-Jacques Girerd; Björn Åkermark (1195-1198).
A new, dinuclear high spin manganese(III) complex with bridging phenoxy and methoxy groups has been prepared. The magnetic properties show that the two manganese ions are ferromagnetically coupled.A new μ-phenoxy-μ-metoxy di-manganese(III) complex with the trisphenolic ligand, 2,6-bis[((2-hydroxybenzyl)(2-pyridylmethyl)amino)methyl]-4-methylphenol, was isolated as a perchlorate salt. The X-ray structure shows that the two manganese(III) ions are in a distorted octrahedral enviroment with approximately perpendicular Jahn–Teller axes. Investigation of the molar magnetic susceptibility reveals a ferromagnetic coupling between the two high-spin manganese(III) ions. Fitting of the data led to g  = 2 and J  = 12.5 cm−1.
Keywords: Manganese complex; X-ray structure; Magnetic properties;

Controllable assembly of an unusual 3-D metallosupramolecular framework with the inclusion of a well-resolved 1-D water morph, and a 2-D layered coordination polymer is described.Two mixed-ligand metal–organic complexes [Cd2(adipato)(phen)2(NO3)2(H2O)2](H2O)6 (1) and {[Cd(adipato)(phen)](H2O)3} n (2) have been synthesized upon the reaction of Cd(II) nitrate with 1,10-phenanthroline (phen) and adipate under similar conditions. For 1, the adipato-bridged dinuclear entities are extended into a 3-D supramolecular architecture via hydrogen bonds and π–π stacking. Interestingly, a well-resolved 1-D water morphology consisting of alternate cyclic water tetramer and hexamer is detected as the guests in each channel of this 3-D lattice. Whereas 2 represents a layered coordination polymer in which the CdII centers are interlinked by adipate dianions via different coordination modes.
Keywords: Controllable assembly; Crystal structure; Host–guest complex; Water cluster; Hydrogen bonding;

Synthesis and structure of the tetradeca-iron(III) oxide–alkoxide cluster [Bu4N]2[Fe14O8(OCH2CH3)20Cl8] by Craig A. Grapperhaus; Martin G. O’Toole; Mark S. Mashuta (1204-1206).
The iron(III) oxide–alkoxide cluster, [Bu4N]2[Fe14O8(OCH2 CH3)20Cl8], has been isolated and structurally characterized. Spectroscopy on the cluster is consistent with oxidation products obtained upon oxygen exposure of iron–thiolate complexes.The iron(III) oxide–alkoxide cluster, di-tetra-n-butylammonium octachloro-tetra(μ3-oxo)-tetra(μ4-oxo)- icosa(μ2-ethoxo)-tetradeca-iron(III), has been isolated and its X-ray crystal structure determined.
Keywords: Iron; Oxo compounds; Alkoxides; Cluster compounds; Sulfur; Oxidation; Oxygen;

Anion-directed assembly of two novel cadmium(II) complexes constructed by 2,2′-(1,4-butanediyl)bis(1H-benzimidazole) ligand by Yong Wang; Hong-Bin Xu; Zhong-Min Su; Kui-Zhan Shao; Ya-Hui Zhao; Hong-Peng Cui; Ya-Qian Lan; Xiang-Rong Hao (1207-1211).
Reaction of cadmium(II) with 2,2′-(1,4-butanediyl)bis(1H-benzimidazole) (abbreviated as H2C4BIm), gives a 1D polymer chain complex with chloride as the counterion and a 2D sheet with 4.82 topology with thiocynate as the counterion. This work demonstrates that different anions used in a reaction may play a major role in the diversity of the products.Depending on the different coordinated anions used, reaction of Cd(II) salt with 2,2′-(1,4-butanediyl)bis(1H-benzimidazole) results in the formation of two coordination polymers: a 1D chain {[Cd(H2C4BIm)Cl2] · (H2C4BIm)} n (1), and a 2D sheet [Cd(HC4BIm)(NCS)] n (2) which features distorted 4.82 topology (H2C4BIm = 2,2′-(1,4-butanediyl)bis(1H-benzimidazole)). The fluorescence properties for both the complexes have been studied.
Keywords: Hydrothermal synthesis; Crystal structure; 4.82 Topology; Fluorescence;

A novel one-dimensional azido-bridged manganese(II) complex has been synthesized and characterized crystallographically and magnetically. Magnetic analysis reveals the weak antiferromagnetic interaction is mediated by the single end-to-end azido bridge.A novel one-dimensional azido-bridged manganese(II) complex of formula [Mn(L)2(N3)](ClO4) 1 has been synthesized and characterized crystallographically and magnetically, where L is the bidentate Schiff base obtained from the condensation of pyridine-2-carbaldehyde with 4-methoxyl aniline. Complex 1 is of one-dimensional chain structure with single end-to-end azido bridges. Magnetic analysis reveals that the weak antiferromagnetic interaction is mediated by the single end-to-end azido bridge with the exchange parameter J  = −6.60 cm−1.
Keywords: Manganese(II); Single end-to-end azide; Magnetic properties; One-dimensional complex;

The bridged μ-hydroxo zinc(II) complex [TtiZn(μOH)ZnTti]ClO4 (2) cleaves the P–O bond in tris(p-nitrophenyl)phosphate, affording a mixture of the monomeric phosphate diester complex TtiZn–OP(O)(OC6H4-p-NO2)2 (3) and phenoxide complex TtiZn–OC6H4-p-NO2 (4). The coordination geometry in both complexes is best described as distorted tetrahedral with an S3O ligand donor set.The bridged μ-hydroxo dinuclear four-co-ordinated zinc(II) complex 2, derived from hydrotris(N-xylyl-2-thioimidazolyl)borate cleaves the P–O bond in tris(p-nitrophenyl)phosphate to form a mixture of a monomeric phosphate diester complex 3 and phenoxo complex 4.
Keywords: S3–zinc(II) complexes; Crystal structure; Phosphate ester; Hydrolysis;

The Kinetics of reduction of [RuIII(tpy)(pic)OH]+ (1) by catechol and ascorbic acid is studied by following the growth of characteristic peak of [RuII(tpy)(pic)H2O]+ (2) at 500 nm.Kinetics of oxidation of catechol (H2cat) to benzoquinone (BQ) and, ascorbate (HA) to dehydroascorbic acid (A) by [RuIII(tpy)(pic)(OH)]+ (1) (tpy = 2,2’6’,2”-terpyridine; pic  = picolinate) have been studied as function of [H2cat] (or [HA]), ionic strength (0.01 − 0.25 M), temperature (10–30 °C) at a constant pH = 3.2, using stopped-flow and rapid-scan diode array spetrophotometric techniques. The rate of reaction of 1 with HA was found to be very fast as compared to that of with H2cat. The kinetic data and activation parameters are interpreted in terms of an associative interchange mechanism. Analysis of spectral and kinetic data revealed that the reaction of 1 with catechol proceeds by a straightforward outer-sphere electron transfer pathway, whereas, reduction of 1 with HA involves ion-pair formation.
Keywords: Ruthenium–tpy complex; Catechol; l-Ascorbic acid; Kinetics and mechanism; Electron transfer;

The 3D framework compound of [Gd2(BDA)3(DMF)2(H2O)4] · 2DMF (1) is constructed from BDA ligands, comprising two kinds of coordination modes, linking up polymeric [GdO5(DMF)(H2O)2] n tethers, and exhibits ferromagnetic interactions between intra-chain GdIII atoms and weak antiferromagnetic interactions between inter-chain GdIII atoms.The open framework compound of [Gd2(BDA)3(DMF)2(H2O)4] · 2DMF (1), prepared by heating GdCl3 with 2,2′-bipyridyl-4,4′-dicarboxylatic acid (BDA) in mixed solvent, is constructed from BDA linking up polymeric [GdO5(DMF)(H2O)2] n tethers. The 1D channels are filled with coordinated and uncoordinated DMF molecules hydrogen bonding to terminal aqua ligands. The study of the temperature dependent magnetic susceptibilities revealed that there are ferromagnetic interactions between intra-chain GdIII atoms and weak antiferromagnetic interactions between inter-chain GdIII atoms.
Keywords: Crystal structure; Ferromagnetic interaction; Functional group; Porous framework; Tether;

An ionic liquid, 1-butyl-3-methylimidazolium bromide, is used as reaction medium for the synthesis and crystallization of a coordination polymer, (BMIM)2[Cd3(BDC)3 Br2] (1) (BMIM = 1-butyl-3-methylimidazolium, BDC = 1,4-benzenedicarboxylate), which forms an anionic two-dimensional framework with the imidazolium cations located between the layers. This compound is thermally stable up to ca. 340 °C and exhibits blue emission in solid state at room temperature.An ionic liquid, 1-butyl-3-methylimidazolium bromide, is used as reaction medium for the synthesis and crystallization of a coordination polymer, (BMIM)2[Cd3(BDC)3Br 2] (1) (BMIM = 1-butyl-3-methylimidazolium, BDC =  1,4-benzenedicarboxylate), which forms an anionic two-dimensional framework with the imidazolium cations located between the layers. This compound is thermally stable up to ca. 340 °C and exhibits blue emission in solid state at room temperature. Other characterizations by IR and UV–visible spectra are also described.
Keywords: Ionic liquid; Imidazolium bromide; Coordination polymer; Blue emission;

Synthesis and crystal structure of Zn[O3PCH(NH2)CH3] · 2H2O, the first zinc α-aminoethylphosphonate with a layer structure by Lian-yi Cui; Zhen-gang Sun; Zhong-min Liu; Wan-sheng You; Zai-ming Zhu; Lei Meng; Hui Chen; Da-peng Dong (1232-1234).
A novel tetrahedrally coordinated zinc phosphonate, Zn[O3PCH(NH2)CH3] · 2H2O, has been synthesized using hydrothermal techniques. X-ray diffraction indicates that this material is a two-dimensional layered structure with the organic part of the phosphonate anion being directed into the interlayer region. The zinc atoms are coordinated by three oxygens of three different phosphonate groups, and by the nitrogen of an additional phosphonate unit.A novel tetrahedrally coordinated zinc phosphonate, Zn[O3PCH(NH2)CH3] · 2H2O, has been synthesized using hydrothermal techniques. X-ray diffraction indicates that this material is a two-dimensional layered structure with the organic part of the phosphonate anion being directed into the interlayer region. The zinc atoms are coordinated by three oxygens of three different phosphonate groups, and by the nitrogen of an additional phosphonate unit.
Keywords: Metal phosphonates; Crystal structure; Hydrothermal synthesis; Zinc;

Treatment of tert-(R) and (S)-[{(N-methyl-N-α- methylbenzyl)amino}methyl]ferrocenes by disodium tetrachloropalladate resulted in the corresponding chiral cyclopalladated ferrocenylamines with the absolute configurations R C,R N,R P and S C, S N,S P, respectively.Condensation of ferrocenylcarboxaldehyde and (R),(S)-α-methylbenzylamines resulted in ferrocenylaldimines 1a, 1b, respectively. Reduction of 1a(b) with lithium aluminum hydride in THF afforded the sec-ferrocenylamines 2a(b). N-Methylation of 2a(b) with sodium cyanoborohydride, formaldehyde and acetic acid yielded the tert-ferrocenylamines 3a(b). Cyclopalladation of 3a(b) with disodium tetrachloropalladate in the presence of sodium acetate produced 4a, b with the absolute configurations R C R N R P and S C S N S P, respectively. The structure of 4a was determined by X-ray single crystal analysis.
Keywords: Ferrocenylamine; N-Methylation; Cyclopalladation; Chirality; Crystal;

Optical sensing of cyanide using hybrid biomolecular films by Keira Poland; Emmanuel Topoglidis; James R. Durrant; Emilio Palomares (1239-1242).
Optical selective sensing of cyanide anions in water is studied using a hybrid biomaterial composed of a mesoporous film of semiconductor nanoparticles and the protein haemoglobin. The picture shows the changes of the UV–vis upon cyanide addition and the colored mesoporous Hb/TiO2 film.The selective sensing of cyanide anions in water has been studied using a hybrid biomaterial composed of a mesoporous TiO2 film of crystalline nanoparticles and the protein hemoglobin. The mesoporous structure of the film prevents protein unfolding and also stabilizes the oxidized form of the prosthetic groups. Low-levels of cyanide anions (<0.2 ppm (0.2 mgr/L)) can be detected by monitoring the changes in the optical properties of the hybrid biomolecular films upon cyanide binding to the heme groups.
Keywords: Bioinorganic chemistry; Mesoporous materials; Cyanide sensing;

Zigzag on a zigzag: Trap of hydrogen-bonded water molecules in a luminescent metal–organic network by Kunlin Huang; Yanting He; Xueli Niu; Xiangyu Chen; Yingnan Chi; Yun Gong; Changwen Hu (1243-1246).
“Zigzag on a zigzag” is observed in a luminescent metal–organic architecture. The arrangement in a zigzag motif of water molecules look as if the motif is projected out of the zigzag motif of CdII atoms via hydrogen bonds. The emission maximum of the title compound is 525 nm.A four-connected 2-D metal–organic coordination polymer {[Cd(mpdc)(phen)] · H2O}(mpdc = 2,6-dimethylpyridine-3,5-dicarboxylate, phen = 1,10-phenanthroline) has been assemblied from cadmium ions and two kinds of organic ligands under hydrothermal conditions, characterized by single-crystal X-ray diffraction analysis. The 2-D metal–organic network was constructed from binuclear [Cd(O5N2)]2 clusters bridged by mpdc2− ligands. The most interesting is that water molecules trapped by the 2-D network look as if its motif is projected from the zigzag arrangement of cadmium atoms in the 2-D network via hydrogen bonding interactions. In addition, new compound exhibits strong luminescence at λ max  = 525 nm upon excitation at 367 nm.
Keywords: Cadmium; Carboxylate; Coordination polymer; Hydrothermal reaction; Luminescence;

The first P–N containing RuCl3NO complex: fac-[RuCl3(NO)(P–N)] (P–N = [o-(N,N-dimethylamino)phenyl]diphenylphosphine) by Deividi A. Cavarzan; Fábio R. Caetano; Lincoln L. Romualdo; Fábio B. do Nascimento; Alzir A. Batista; Javier Ellena; Andersson Barison; Márcio P. de Araujo (1247-1250).
The first P–N containing {RuNO}6 was obtained starting from [RuCl3(H2O)2(NO)]. The fac-isomer was isolated from the reaction and was characterized by NMR (31P, 1H, 13C), ESI-MS, elemental analysis and cyclic voltammetry.Complex fac-[RuCl3(NO)(P–N)] was synthesized from [RuCl3(H2O)2(NO)] in methanol solution under reflux. The orange solid obtained was characterized by NMR (31P{1H}, 1H, 13C) and, cyclic voltammetry, ESI-MS, IR, elemental analysis and X-ray diffraction structure determination. The 31P{1H} reveals the presence of singlet at 36 ppm. IR N–O stretching as KBr pellets or CH2Cl2 solution presented 1866 cm−1 and 1872 cm−1, respectively.
Keywords: Nitrosyl ruthenium; P–N ligand; X-ray structure;

Self-assembly through hydrogen-bonding and C–H⋯π interactions in metal complexes of N-functionalised glycine by Nilotpal Barooah; Anirban Karmakar; Rupam J. Sarma; Jubaraj B. Baruah (1251-1254).
Different types of self-assemblies through hydrogen-bonding and C–H⋯π interactions in metal complexes of N-functionalised glycine are discussed. The complex [Ni(L1)2(py)2]. toluene (L1 is N-phthaloyl glycinato and py is pyridine) was prepared from solid state reaction whereas co-crystals having composition 2[Ni(L1)2(py)3(H2O)] · [Ni(L1)2(py)2(H2O)2] · 2py · 2H2O was obtained from solution state reaction.The complex [Ni(L1)2(py)2]. toluene (L1 is N-phthaloylglycinato and py is pyridine) was prepared from solid state reaction whereas co-crystals having composition 2[Ni(L1)2(py)3(H2O)] · [Ni(L1)2(py)2(H2O)2] · 2py · 2H2O was obtained from solution state reaction.
Keywords: Self-assembly; Co-crystals; Glycine derivatives; Metal complexes; C–H⋯π interactions;

Ferrocene pincer ligands made easy by Ian R. Butler; Benjamin Woldt; Min-Zae Oh; Denis J. Williams (1255-1258).
A simple and effective methodology has been developed to allow the synthesis of a broad range of 1,3-disubstituted ferrocenesA simple and effective two step synthesis of ferrocene pincer ligands is described starting from readily available N,N-dimethylaminomethylferrocene.
Keywords: Pincer; Ferrocene; Ligand;

A 3D PbII coordination polymer containing 1,2,4-triazole (trz) and two different anions, [Pb2(trz)2(CH3COO)(NO2)] n has been synthesized and characterized by elemental analysis, IR, 1H NMR, 13C NMR spectroscopy and studied by thermal as well as X-ray crystallography. The single-crystal X-ray data shows two types of Pb2+-ions with coordination numbers of seven, Pb(1) and Pb(2) with hemidirected and holodirected geometries, respectively..A 3D PbII coordination polymer containing 1,2,4-triazole (trz) and two different anions, [Pb2(trz)2(CH3COO)(NO2)] n has been synthesized and characterized by elemental analysis, IR-, 1H NMR-, 13C NMR spectroscopy and studied by thermal as well as X-ray crystallography. The single-crystal X-ray data shows two types of Pb2+-ions with coordination numbers of seven, Pb(1) and Pb(2) with hemidirected and holodirected geometries, respectively.

A new photoluminescent copper(I) polymer [(Cu6Br6)(bix)3] n (bix = 1,4-bis(imidazole-l-ylmethyl)benzene) (1) has been hydrothermally synthesized and structurally characterized. The structure of 1 features a ‘ interpenetrating network which contains a [Cu3(bix)3] n chain structure and a novel (Cu3Br6) cluster unit acting as a T-shaped module.A new photoluminescent copper(I) polymer [(Cu6Br6)(bix)3] n (bix = 1,4-bis(imidazole-l-ylmethyl)benzene) (1) has been hydrothermally synthesized and structurally characterized. The structure of 1 features a 3D interpenetrating network with a novel (Cu3Br6) cluster unit acting as a T-shaped module. The present compound was characterized using IR, Elemental analysis and X-ray single-crystal analysis. The photoluminescent property of the title compound was also investigated.
Keywords: Copper(I) polymer; Photoluminescent property; Flexible N-donor ligand; Bix ligand; Hydrothermal synthesis;

Synthesis and characterization of novel N-para-ferrocenyl benzoyl dipeptide esters by David Savage; Steven R. Alley; Alok Goel; Tara Hogan; Yoshiteru Ida; Paula N. Kelly; Laurent Lehmann; Peter T.M. Kenny (1267-1270).
N-para-ferrocenyl benzoyl dipeptide ethyl esters 25 have been prepared by coupling para-ferrocenyl benzoic acid 1 to the dipeptide ethyl esters GlyGly(OEt) 2, GlyAla(OEt) 3, GlyLeu(OEt) 4 and GlyPhe(OEt) 5 using the conventional 1,3-dicyclohexylcarbodiimide (DCC), 1-hydroxybenzotriazole (HOBt) protocol. The compounds were structurally characterized by a combination of NMR spectroscopic techniques and tandem mass spectrometry (MS/MS). The a1 and b1 ions appeared at one mass unit less than the expected mass in the tandem mass spectra. The CV curves of compounds 25 exhibited quasi-reversible redox behaviour. N-para-ferrocenyl benzoyl dipeptide esters 25 were prepared by coupling para-ferrocenyl benzoic acid 1 to the dipeptide ethyl esters GlyGly(OEt) 2, GlyAla(OEt) 3, GlyLeu(OEt) 4 and GlyPhe(OEt) 5. The compounds were fully characterized by a range of NMR spectroscopic techniques, mass spectrometry (ESI-MS, FABMS, MS/MS) and cyclic voltammetry (CV). The a1 and b1 ions appeared at one mass unit less than the expected mass in the tandem mass spectra. The CV curves of compounds 25 exhibited quasi-reversible redox behavior similar to the Fc/Fc+ redox couple and displayed oxidation potential values in the 50–55 mV range, against the Fc/Fc+ redox couple.
Keywords: Ferrocene; Bioorganometallic chemistry; Tandem mass spectrometry; Dipeptides; CV;

Pyrazole-based allylpalladium complexes: Supramolecular architecture and liquid crystal behaviour by M.C. Torralba; M. Cano; J.A. Campo; J.V. Heras; E. Pinilla; M.R. Torres (1271-1275).
Mesomorphic properties of allylpalladium complexes based on 3-alkyloxyphenylpyrazole ligands are determined. Lamellar mesophases SmA are established at temperatures between ca. 40 and 80 °C. The X-ray structure of one of the studied compounds is described, showing interdigitated layer-like supramolecular arrangement.The co-ordination of non-mesomorphic 3-substituted pyrazoles HpzR to the [Pd(η 3-C3H5)]+ fragment gives rise to four-coordinated complexes [Pd(η 3-C3H5)(HpzR)2]+ (R = C6H4OC n H2n+1; n  = 12 (I 12), 14 (I 14), 16 (I 16), 18 (I 18)), which were isolated with BF 4 - as counteranion. The new complexes are proved to have liquid crystal properties exhibiting monotropic or enantiotropic smectic A (SmA) mesophases at low temperatures which range between ca. 40 and 80 °C. The crystal structure of I 12 presents a 2D network highly interdigitated, which could be related with the layered structure proposed in the liquid crystalline phase through the X-ray diffraction at variable temperature.
Keywords: Palladium(II) complexes; Pyrazole; Metallomesogen; X-ray structure;

Ferromagnetic mixed tribridged dinuclear copper(II) complex [Cu2(OAc)2(OH)(dpa)2] PF6  · H2O(dpa = 2,2′-dipyridylamine): 3D superstructure based on hydrogen bond and π…π interaction A dinuclear complex[Cu2(OAc)2(OH)(dpa)2] PF6  · H2O (1) is prepared and structurally and magneto-structurally characterized. The monocationic core contains one acetate in familiar bidentate η112- bridge and another in the rare monoatomic bridge along with one hydroxo intermediary. Compound 1 packs through N–H…O and O–H…O hydrogen bonds and π…π interaction resulting a 3D supramolecular continuum and displays high-energy intraligand 1(π−π*) fluorescence and intraligand 3(π−π*) phosphorescence in glassy solutions.A new dinuclear complex [Cu2(OAc)2(OH)(dpa)2] PF6  · H2O (1) is prepared and structurally and magneto-structurally characterized. The monocationic core contains one acetate in familiar bidentate η112-bridge and another in the rare monoatomic bridge along with one hydroxo intermediary. 1 packs through N–H…O and O–H…O hydrogen bonds and π…π interaction resulting a 3D supramolecular continuum and displays high-energy intraligand 1(π − π*) fluorescence and intraligand 3(π − π*) phosphorescence in glassy solution.
Keywords: Dinuclear copper(II); 2,2′-Dipyridylamine; Superstructure; Ferromagnetism; Luminescence;

An unprecedented Keggin-type tungstogermanate dimer bearing dinuclear copper-organic coordination ions {H8[Cu(phen)(μ2-CH3COO)2Cu(phen)(H2O)]2[Ge2W23CuO80]} · 24H2O is built up from a dimeric heteropolyanion constituted by two corner-shared Keggin-type building subunits and two dinuclear copper-organic coordination cations [Cu(phen)(μ2-CH3COO)2Cu(phen)(H2O)]2+, each of which consists two square pyramidal copper-phen ions bridged by two μ2-acetate ligands.An unprecedented Keggin-type tungstogermanate dimer bearing dinuclear copper-organic coordination ions {H8[Cu(phen)(μ2-CH3COO)2Cu(phen)(H2O)]2[Ge2W23CuO80]} · 24H2O has been synthesized and characterized by IR, UV, ICP analyses, ESR spectra, element analysis, TG and single crystal X-ray diffraction analysis. The compound is built up from a dimeric heteropolyanion constituted by two corner-shared Keggin-type building subunits and two dinuclear copper-organic coordination cations [Cu(phen)(μ2-CH3COO)2Cu(phen)(H2O)]2+, each of which consists two square pyramidal copper-phen ions bridged by two μ2-acetate ligands.
Keywords: Polyoxometalate; Organic–inorganic hybrid materials; Tungsten; Germanium; Copper; Keggin structure;

Unusual iron-mediated C–N bond formation and synthesis of the Fe(III) complex of a polypyridine ligand with one carboxamide group by Raman K. Afshar; Kirsten E. Granados; Marilyn M. Olmstead; Pradip K. Mascharak (1286-1288).
An Fe(III) chloro complex, [(PaPPy3)Fe(Cl)](ClO4) (where PaPPy 3 - = deprotonated N,N-bis(2-pyridylmethyl)amine-N-propyl-2-pyridine-2-carboxamide), derived from a pentadentate polypyridine N5 ligand containing one carboxamide group has been synthesized in situ via the template effect.A high-spin iron(III) chloro complex [(PaPPy3)Fe(Cl)](ClO4) (1, where PaPPy 3 - =N,N-bis(2-pyridylmethyl)amine-N-propyl-2-pyridine-2-carboxamide) has been synthesized via the “template effect” and structurally characterized. The template reaction leads to the formation of a new carbon–nitrogen bond from coupling of a primary alkyl chloride with a secondary amine.
Keywords: Iron(III); N ligands; Carboxamido nitrogen; Template effect; Crystal structure;

An unexpected sulfinate–sulfonate mixed coordination polymer of copper(II) by Salomé Delgado; Agustín Molina-Ontoria; Manuela E. Medina; Cesar J. Pastor; Reyes Jiménez-Aparicio; José L. Priego (1289-1292).
A new one-dimensional polymer containing 2-pyridine sulfinate and 2-pyridine sulfonate species was obtained by reaction of copper nitrate trihydrate and 2,2′-dipyridyldisulfide. The magnetic properties have been studied.By reaction of copper nitrate trihydrate and 2,2′-dipyridyldisulfide in both aerobic and anaerobic conditions, the mixed [{Cu(2-pySO2)2} n ]–[{Cu(2-pySO3)2} n ] coordination polymer of copper(II) (1) has been synthesized. The X-ray diffraction analysis indicates that complex 1 exhibits an infinite one-dimensional polymeric chain consisting of [Cu(C5H4N)2] building units connected by SO2/SO3 groups. The atom which has been labelled O3 is only present in 60% of the molecules. Complex 1 exhibits a very weak ferrogmagnetic spin coupling (zJ  = +0.40 cm−1).
Keywords: Coordination polymers; Copper; N ligands;

Terminal ligand effect on the structure variation of Copper(II) complexes by Bin Zhai; Wei-Zheng Shen; Xiao-Yan Chen; Hai-Bin Song; Wei Shi; Peng Cheng (1293-1296).
Two copper(II)–poly(pyrazolyl)methane complexes [Cu2(bpm)4(ta)](ClO4)2  · 2H2O 1 and {[Cu2(tpm)2(ta)2] · H2O} n 2 (bpm = bis(3,5-dimethylpyrazolyl)methane, tpm = tris(pyrazolyl)methane, H2ta = terephthalic acid) were synthesized and characterized. 1 is a binuclear complex, while 2 exhibits as a 1D zigzag coordination polymer.Two copper(II)–poly(pyrazolyl)methane complexes [Cu2(bpm)4(ta)](ClO4) 2  · 2H2O 1 and {[Cu2(tpm)2(ta)2] · H2O} n 2 (bpm = bis(3,5-dimethylpyrazolyl)methane, tpm = tris(pyrazolyl)methane, H2ta = terephthalic acid) were synthesized and characterized by elemental analysis, FT-IR and UV–vis spectra. 1 is a binuclear complex, while 2 exhibits as a 1D zigzag coordination polymer.
Keywords: Bis(3,5-dimethylpyrazolyl)methane; Tris(pyrazolyl)methane; Terephthalic acid; Copper(II) complex; Crystal structure;

A new NiIICuIICuIINiII complex was synthesized by using azido bridging ligand and a macrocyclic complex ligand, and was structurally characterized by X-ray crystallography. The magnetic behavior of the complex shows ferromagnetic interactions between the two copper ions through the double end-on azido bridges.[Cu2(NiL)2(N3)4] was synthesized by combining “complex as ligand” approach and “pure bridging ligand” approach (H2L = dimethyl 5,6,7,8,15,16-hexahydro-15-methyl-6,7-dioxodibenzo[1,4,8,11]tetraazacyclotetradecine-13,18-dicarboxylate). The two CuII ions are bridged by two end-on azido ligands. π⋯π and oxamido–carbonyl interactions link the molecules into 1D supramolecular chains. Ferromagnetic interactions exist between the two CuII ions.
Keywords: Synthesis; Crystal structure; Magnetism; Azido bridge; Macrocyclic complex ligand; Intermolecular interaction;

The complexes [ML(NNNR)]+ {M = Pd, Pt; L = Cl, CH3; SO3CH3; NNNR  = tridentate chelate ligands} were prepared by metal-assisted condensation of 8-aminoquinoline and an ortho-substituted aldehydo- or keto-pyridine. Information about the formation of these complexes, obtained by NMR measurements, are reported.The complexes [PtCl(NNNH)](OTf) (1 H ), [PdCl(NNNH)](OTf) (2 H ), [PdCl(NNNMe)](OTf) (2 Me ), [PdMe(NNNH)](OTf) (3 H ), [PdMe(NNNMe)](OTf) (3 Me ) and [PdMe(NNNPh)](OTf) (3 Ph ) {NNNH  = (pyridin-2-ylmethylene)-quinolin-8-yl-amine; NNNMe  = (1-pyridin-2-yl-ethylidene)-quinolin-8-yl-amine; NNNPh  = (phenyl-pyridin-2-yl-methylene)-quinolin-8-yl-amine} were prepared by reacting a stoichiometric methanolic mixture of 8-aminoquinoline and an ortho-substituted aldehydo- or keto-pyridine {2-pyridinecarboxaldehyde, 2-acetylpyridine or 2-benzoylpyridine} with the proper Pt(II) or Pd(II) precursor in methanol. In the case of the 2 Me derivative, the addition of a stoichiometric amount of a Ag(I) salt to the reaction mixture was necessary to obtain the desired product. Information about the formation of these complexes are reported. In particular, NMR experiments allowed to observe the different reactivity of 8-aminoquinoline towards aldehydo- and keto-pyridines and the formation of the emiaminal ligand pyridin-2-yl-(quinolin-8-ylamino)-methanol NNN(H2O)H 4. Finally, the methanesulphonato-complex [Pd(η1-OSO2CH3)(NNNMe)](OTf) (5 Me ) was obtained by reacting the chloro-derivative 2 Me with a stoichiometric amount of AgSO3CH3 in nitromethane.
Keywords: Palladium; Platinum; Schiff bases; N-donor chelates; Metal-assisted synthesis; Methyl-complexes; Chloro-complexes;

Synthesis and characterization of a novel 3D copper(I) coordination polymer with a ligand generated in situ by Xi-He Huang; Tian-Lu Sheng; Sheng-Chang Xiang; Rui-Biao Fu; Sheng-Min Hu; Ya-Min Li; Xin-Tao Wu (1304-1307).
Hydrothermal reaction of CuCl2  · 2H2O, NaN3 with 1,4-dicyanobenzene in water/ethanol yielded a novel Cu(I)-tetrazolate, {Cu(cptz)} n , (1) (Hcptz is 5-(4-cyanophenyl)-tetrazole). The cptz ligand in the complex was generated in situ through the [2 + 3] cycloaddition reaction involving one of the two cyano-groups of the precursor 1,4-dicyanobenzene. The structure characterization shows that 1 possesses a 3D 4-connected SrAl2 topological network.Hydrothermal reaction of CuCl2  · 2H2O, NaN3 with 1,4-dicyanobenzene in water/ethanol yielded a novel Cu(I)-tetrazolate, {Cu(cptz)} n , (1) (Hcptz is 5-(4-cyanophenyl)-tetrazole). The cptz ligand in the complex was generated in situ through the [2 + 3] cycloaddition reaction involving one of the two cyano-groups of the precursor 1,4-dicyanobenzene. The structure characterization shows that 1 possesses a 3D 4-connected SrAl2 topological network. Additionally, complex 1 exhibits strong yellow fluorescence at room temperature in the solid state.
Keywords: Copper; Tetrazolate; In situ; Hydrothermal synthesis; Coordination polymer;

A novel polyoxometalate chain constructed from sandwich lanthanide-containing polyanion [Ce(PW11O39)2]10− and sodium ion linker by Lihua Fan; Lin Xu; Guanggang Gao; Fengyan Li; Zhikui Li; Yunfeng Qiu (1308-1311).
A new sandwich-type lanthanide polyoxometalate (NH4)2[N(CH3)4]6Na2[Ce(PW11O39)2] · 14H2O (1), in which sodium ions is used as linker to form a zigzag chain structure, and each [α- PW11O39]7− anion acts as a four-dentate ligand to coordinate with the CeIV metal center.A novel sandwich-type lanthanide polyoxometalate (NH4)2[N(CH3)4]6Na2[Ce(PW11O39)2] · 14H2O (1) has been synthesized and characterized by cyclic voltammetry, IR spectroscopy and single crystal X-ray diffraction. X-ray diffraction result reveals that the sandwich-type polyanions are linked by sodium ions to form a structure of zigzag chains, and the chains are further connected into an extensive two-dimensional (2D) framework depending on hydrogen bond.
Keywords: Polyoxometalate; Lanthanide; Sandwich; Chain; Framework;

1D neutral double helical cyanide-bridged copper(I) coordination polymer [Cu3(CN)3(phen)] n with (phen)Cu–CN– side-arms as interchain bridges, was synthesized and structurally and fluorescent characterized.Hydrothermal reaction of CuCN, K3[Fe(CN)6] and 1,10-phenanthroline affords a novel cyanide-bridged copper(I) coordination polymer [Cu3(CN)3(phen)] n (1). The complex displays an interesting one-dimensional neutral double helical framework with (phen)Cu–CN– side-arms as interchain bridges. The double helical chains are close packed in a parallel fashion, and the phen ligands stack in an interpenetrating mode, which leads to π–π interactions between parallel phen planes. The thermal stability and fluorescent property have also been investigated.
Keywords: Copper(I) cyanide; Coordination polymer; Hydrothermal synthesis; Double helix; Crystal structure; Fluorescence;

Synthesis, characterization, and crystal structures of two new polyoxomolybdate wheel clusters by Zhen-He Xu; Yang-Guang Li; En-Bo Wang; Chao Qin; Xin-Long Wang (1315-1318).
Two new polyoxomolybdates Na5(NH4)16[Mo57Mn6(NO)6O174(OH)3(H2O)24] · 44H2O (1) and (NH4)21[Mo57Cu6(NO)6O168(OH)3(H2O)24] · 53H2O (2) were synthesized in aqueous solution and characterized by elemental analysis, IR, TG analysis and single-crystal X-ray diffraction. They represent interesting examples of integrating and embedding magnetic 3d metal ions into the diamagnetic polyoxomolybdate host structure.Two new polyoxomolybdates Na5(NH4)16[Mo57Mn6(NO)6O174 (OH)3(H2O)24] · 44H2O (1) and (NH4)21[Mo57Cu6(NO)6O168(OH)3(H2O)24] · 53H2O (2) were synthesized in aqueous solution and characterized by elemental analysis, IR, TG analysis and single-crystal X-ray diffraction. They represent interesting examples of integrating and embedding magnetic 3d metal ions into the diamagnetic polyoxomolybdate host structure.
Keywords: Polyoxometalates; Transition metal; Crystal structure; Magnetic;

Synthesis and molecular structure of the sodium arsanediyl zincate [(thf)Na]2[(EtZn)6(AsSiiPr3)4] by Matthias Westerhausen; Gerhard Sapelza; Peter Mayer (1319-1321).
The deprotonation of H2AsSiiPr3 and NaAs(H)SiiPr3 at the same time by ZnEt2 gives the deep red sodium arsanediyl zincate 1. This cage compound consists of 6 Zn and 4 As atoms, the Zn atoms are arranged in a twist-cyclo-hexazincahexane conformation (Zn blue, As orange, Na green, O red, and Si grey).The reaction of NaAs(H)SiiPr3 with ZnEt2 in the presence of additional triisopropylsilylarsane yields the heterobimetallic complex [(thf)Na]2 [(EtZn)6(AsSiiPr3)4] (1) in the shape of red prisms. The Na–As and Zn–As bond lengths show values of 301/309 pm and between 247 and 260 pm, respectively.
Keywords: Sodium; Zinc; Arsanides; Cage compounds; Metallation reactions;

Bimetallic salicylaldimine-nickel complex 2b can be used as high active catalyst for ethylene polymerization to afford polymer with high molecular weight and broad molecular weight distribution.Bimetallic salicylaldimine-nickel complexes, 2,4,6-Me3-1,3-{[N=CH–(3′-R-5′-Y-2′-O–C6H3)-κ 2-N,O]Ni(Ph) (PPh3)}2 [R =  tert-Bu, Y = Me, 1b; R = Ph, Y = H, 2b] were prepared and their catalytic behaviors of ethylene polymerization were investigated. The bimetallic complex 2b shows higher activities (2.9 × 105  g PE mol−1  Ni h−1) for ethylene polymerization and affords polymer with high molecular weight (M w  = 1.41 × 105) and broad molecular weight distribution (M w/M n  = 6.1) than its mononuclear matrix, {[(2,6-Me2C6H3)–N=CH–(3′-Ph-2′-O–C6H3)-κ 2-N,O]Ni(Ph)(PPh3)} (3) (Activity = 5.5 × 104  g PE mol−1  Ni h−1; M w  = 1.86 × 104; M w/M n  = 2.8).
Keywords: Nickel; Dinuclear; Catalyst; Ethylene polymerization; Molecular structure;

Two new polymorphs of [Ni(pyridine)4(NCS)2] and its unique macro-ionic derivative [ ( N -methylpyridinium ) n ] 2 2 n + · [ Ni ( μ 1 , 3 – SCN ) 2 ( NCS ) 2 ] n 2 n - with effective conductivity value (205  Λ M ) are reported.Solvothermal treatment of [Ni(pyridine)4(NCS)2] in the presence of 4,5-imidazoledicarboxylic acid allows the isolation of two new polymorphs depending on solvents (CH3CN or CH3CN/CH3OH). Furthermore, one unusual conductive macro-ionic complex [ ( N -methylpyridinium ) n ] 2 2 n + · [ Ni ( μ 1 , 3 – SCN ) 2 ( NCS ) 2 ] n 2 n - is obtained when the reaction is carried out in CH3OH, providing a new insight into polymorphism and reactivity of [Ni(pyridine)4(NCS)2].
Keywords: Thiocyanate; Polymorphism; Reactivity; Conductivity; Macro-ionic complex; Structure;

Polyoxotungstates containing uranyl group: Germanotungstates with Keggin sandwich structure by Rongxin Tan; Xiaohong Wang; Fang Chai; Yaqian lan; Zhongmin Su (1331-1334).
Two new sandwich structure of polygermanotungstates containing uranyl groups A-α-Na14[Na2(UO2)2(GeW9O34)2] · 48H2O and A-β-Na14[Na2(UO2)2(GeW9O34)2] · 42H2O were synthesized and their structures investigated by elemental analysis, IR and single-crystal X-ray diffraction.Two new polygermanotungstates containing uranyl group A-α-Na14[Na2(UO2)2(GeW9O34)2] · 48H2O (1) and A-β-Na14[Na2(UO2)2(GeW9O34)2] · 42H2O (2) have been synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. Both the two polyanions consist of two [GeW9O34]10− units which sandwich two UO 2 2 + cations and two Na+ cations. The two uranium atoms are similar to each other, that is, each uranium is pentagonal–bipyramidal coordination achieved by three equatorial U–O bonds to one GeW9O34 and two U–O bonds to the other.
Keywords: Polyoxometalates (POMs); Uranyl group; Sandwich structure; Pentagonal–bipyramidal coordination;