Inorganic Chemistry Communications (v.5, #11)

Contents List (iii-iv).

Synthesis and transition metal coordination of 2-(azidomethyl) phenyl isocyanide by Giacomo Facchin; Rino A. Michelin; Mirto Mozzon; Sandra Pugliese; Paolo Sgarbossa; Augusto Tassan (915-918).
The reaction of 2-(chloromethyl)phenyl formamide, 2-(CH2Cl)C6H4NHCHO, with NaN3 in DMSO at room temperature affords 2-(azidomethyl)phenyl formamide, 2-(CH2N3)C6H4NHCHO (1), which is then dehydrated to 2-(azidomethyl)phenyl isocyanide, 2-(CH2N3)C6H4NC, (2) upon reaction with SOCl2 in DMF at low temperature. The coordination ability of the isocyanide 2 has been tested towards some Pt(II), Pd(II) and W(0) metal complexes to yield derivatives of the type [PtCl2(CNC6H4-2-CH2N3)2], [PdCl2(CNC6H4-2-CH2N3)(PPh3)] and [W(CO)5(CNC6H4-2-CH2N3)], respectively.
Keywords: Isocyanide; Functionalized isocyanide; Azido; Transition metal complexes;

Photoluminescence characteristics and mechanism of SrAl2O4 co-doped with Eu3+ and Cu2+ by Ping Yang; Meng Kai Lü; Chun Feng Song; Dong Xu; Duo Rong Yuan; Guang Ming Xia; Su Wen Liu (919-923).
SrAl2O4 co-doped with Cu2+ and Eu3+ was prepared at high temperature in a weakly oxidizing atmosphere by solid states reaction. X-ray diffraction (XRD) pattern of the sample shows that the doped sample exhibits SrAl2O4 crystalline phase. No characteristic peaks of dopant have been observed in XRD pattern of doped sample. The excitation and emission spectra of CuEu:SrAl2O4, Eu:SrAl2O4, Cu:SrAl2O4 samples consist of many sharp peaks. The excitation and emission spectra of the SrAl2O4 sample co-doped with Cu2+ and Eu3+ are significantly different from those of Eu:SrAl2O4 and Cu:SrAl2O4 samples. The novel photoluminescence (PL) characteristic of the co-doped sample is attributed to the composite luminescence of Cu2+ and Eu3+ ions in SrAl2O4 matrix.
Keywords: SrAl2O4; Doped; Cu2+ and Eu3+; Photoluminescence;

Mono-, di- and tri-nuclear Ni(II) complexes of N-, O-donor ligands: structural diversity and reactivity by Mishtu Dey; Chebrolu P. Rao; Pauli K. Saarenketo; Kari Rissanen (924-928).
A series of mono-, di- and tri-nuclear Ni(II) complexes of N, O-donating molecules possessing H2CNH and HCN moieties have been synthesized and characterized and the structures have been determined by single crystal X-ray diffraction. All these exhibited interesting molecular packing in their crystal lattices. Di-nuclear complexes were found to be cleaved in pyridine to result in mononuclear ones with additional coordinations being provided by pyridine. Di-nuclear complexes were found to form urea adducts as demonstrated based on absorption and vibrational studies.
Keywords: Mono-, di- and tri-nuclear Ni(II) complexes; Urea adduct; Pyridine bound mononuclear Ni(II) complex; N-, O-donor molecules;

A novel zinc(II) coordination polymer [Zn(fca)2(bpe)] n ·2nH2O (bpe=1,2-bis(4-pyridyl)ethene, fca=C5H5FeC5H4C(OH)CHCOCH3) was obtained by the reaction of Zn(OAc)2·2H2O with bpe and 1-ferrocenylbutane-1,3-dione (ferrocenoylacetone, Hfca) in methanol solution. X-ray structural analysis reveals that the compound contains two kinds of ligands: one is the 1,2-bis(4-pyridyl)ethene ligand, directly bridging zinc(II) centers to form a one-dimensional chain [Zn(bpe)] n , the other is the enolized ferrocenylacetone chelating the central ion. The zinc(II) ion is in an elongated octahedral environment with four oxygen atoms from two distinct enolized ferrocenoylacetone, two nitrogen atoms of the bridging 1,2-bis(4-pyridyl)ethene ligands.A novel coordination polymer [Zn(fca)2(bpe)] n ·2nH2O was obtained by the reaction of Zn(OAc)2·2H2O with ferrocenoylacetone and 1,2-bis(4-pyridyl)ethene. X-ray structural analysis reveals that 1,2-bis(4-pyridyl)ethene ligands directly bridge zinc ion centers forming a one-dimensional chain [Zn(bpe)] n , and two enolized ferrocenylacetones chelate the central ion at the same time. Each zinc(II) ion is in an elongated octahedral environment.
Keywords: Coordination polymer; Zinc(II); Ferrocenoylacetone; 1,2-Bis(4-pyridyl)ethene;

Synthesis of nano-fibrillar bismuth sulfide by a surfactant-assisted approach by Qing Li; Mingwang Shao; Ji Wu; Guihua Yu; Yitai Qian (933-936).
Bi2S3 nanofibers with a diameter less than 10 nm and lengths ranging from 400 to 1000 nm were successfully prepared by a convenient solution route at 90 °C by using BiCl3 and thiourea as the starting materials. The product was characterized by XRD, XPS, and TEM techniques. It was found that anionic surfactant C17H33COOK played an important role in controlling the morphology of the product. The formation of the nanofibers could be well explained by the accordion-like folding mechanism.
Keywords: Bismuth sulfide; Nanofiber; Surfactant; Ethylene glycol;

Substitution behaviour of an unusual seven-coordinate iron(III) complex in different solvents by Ivana Ivanovic-Burmazovic; Mohamed S.A. Hamza; Rudi van Eldik (937-940).
In order to clarify the solution chemistry of 3d metal hepta-coordinate complexes, a detailed mechanistic study of the two-step substitution reaction between the “tweezer-like” iron(III) complex, [Fe(dapsox)(H2O)2]+ (H2dapsox=2,6-diacetylpyridine-bis-(semioxamazide)), and SCN was performed in water and methanol as solvents. Based on the observed rate law and reported activation parameters (ΔH #, ΔS # and ΔV #) for both reaction steps in aqueous solution, the operation of an I a mechanism for the diaqua, an I d mechanism for the aquathiocyanato, and an I d or D mechanism for the aquahydroxo forms of the Fe(III) complex, is proposed. The operation of a limiting D mechanism is proposed for both reaction steps in methanol as solvent.
Keywords: Seven-coordinate complexes; Fe(III); Mechanisms; High pressure;

Half-sandwich ruthenium complexes for the controlled radical polymerisation of vinyl monomers by Oscar Tutusaus; Sébastien Delfosse; François Simal; Albert Demonceau; Alfred F Noels; Rosario Núñez; Clara Viñas; Francesc Teixidor (941-945).
Ruthenium complexes of the type [RuX(Cp#)(PPh3)2] (X=Cl and H; Cp#=Cp, Cp*, indenyl, and carboranyl) catalyse the radical polymerisation of styrene and n-butyl acrylate, and both the catalyst activity and the degree of control of the polymerisation strongly depend on the Cp# ligand and the monomer.
Keywords: Homogeneous catalysis; Olefins; Polymerisations; Radical reactions; Ruthenium and compounds;

The interaction of Co(acac)2with Al(O i Pr)3 in 1:1 ratio in toluene on reflux provided with quantitative yield a new heterometallic heteroleptic alkoxide complex, Co 2 Al 2(O i Pr)6(acac)4 (I), displaying the so far unprecedented linear chain structure with a M(μ-OR)2M(μ-OR)2M(μ-OR)2Mcore. I appears to be a promising precursor for cobalt oxide–cobalt spinel nanocomposite materials.
Keywords: Heterometallic alkoxides; Late transition metal alkoxides; Alkoxoaluminates; Co spinel; X-ray study;

The reduction reaction of Cu(II)L by decamethylferrocene, where L is quadridentate 1,2-bis(9-methyl-1,10-phenanthrolin-2-yl)ethane, was examined in acetonitrile. We observed parallel gated electron transfer pathways: (1) regulated by the unimolecular deformation within Cu(II)L, and (2) regulated by the bimolecular dimerization to form Cu(II)2L2, prior to the electron transfer process with decamethylferrocene.
Keywords: Gated electron transfer; Copper complex; Quadridentate ligand; Monomer/Dimer interconversion;

The preparation of a silver triflate complex (5) of 1,3-bis(8-quinolyloxymethyl)benzene (4) is described. An X-ray crystal structure determination reveals that it is a compact circular helicate in which three silver atoms are bridged by three ligands in a cyclic array, with additional stabilisation via intramolecular π–π stacking interactions.

Monomeric and dimeric metal complexes of a simply prepared and versatile pentapyridyldiamine by David G. Lonnon; Donald C. Craig; Stephen B. Colbran (958-962).
The new pentapyridyldiamine, BPA-TPA, is easily made and has been used to prepare [Cu2(BPA-TPA)Br2]2Br2[Cu2Br4] and [Fe(BPA-TPA)](ClO4)2. The crystal structures of these complexes reveal BPA-TPA to be a versatile ligand, for example, capable of bridging two metal centres in chiral [Cu22-BPA-TPA)Br2]2 2+ ‘wedges’ or wrapping about a larger metal ion to give novel homoleptic seven co-ordinate species such as the chiral [Fe(κ7N-BPA-TPA)]2+ ion.
Keywords: Heptadentate pyridine-amine ligand; Iron complexes; Copper complexes; Crystal structures;

Optically active complexes (μ-H)Os3(μ-OCNH-(R)-CHMePh)(CO)10: the absolute configuration of the (+)-rotating stereoisomer by Victoria A. Ershova; Alexander V. Virovets; Vladimir M. Pogrebnyak; Anatoly V. Golovin (963-965).
Room-temperature interaction between Os3(CO)11NCMe and (R)-(+)-1-phenylethylamine at ambient temperature in THF gives two known diastereomeric clusters (μ-H)Os3(μ-OCNH-(R)-CHMePh)(CO)10 in an approximate ratio 1:2. 1H-NMR, IR and [α] D characteristics are described for them. The (+)-diastereomer characterized by absolute-configugational data obtained from the X-ray analysis of its single crystal.
Keywords: Triosmium chiral clusters; Absolute configuration; X-ray analysis;

n=2 Member of the hexagonal perovskite-intergrowth manganate family A n+1Mn n O3n+3(Ca2O) by Lijian Bie; Jianhua Lin; Yingxia Wang; Chun-K. Loong (966-970).
The n=2 member in hexagonal perovskite manganate family A n+1Mn n O3n+3(Ca2O) was obtained in a complex composition La2Ba0.8Sr0.6Ca1.6Mn2O10, but simple hexagonal structure. It crystallizes in the hexagonal P63/mmc space group [a=5.63591(5)  A ̊ , c=16.2843(3)  A ̊ , V=447.948(9)  A ̊ 3 ; Z=2] and consists of double hexagonal perovskite layers (2H-type) and graphite-like [Ca2O] layer. The manganese octahedra share faces resulting in localized magnetic property.
Keywords: Hexagonal-perovskite intergrowth manganate; Solid state;

A metal-reduction route to synthesis of nickel nanotubules by Meining Wu; Yongchun Zhu; Huagui Zheng; Yitai Qian (971-974).
Nickel nanotubule was synthesized using reduction of nickel chloride by metallic zinc in aqueous solution in presence of ethanol amine at room temperture. X-ray diffraction (XRD) and electron diffraction showed that the as-prepared nanotubules were nickel with a face centered cubic structure. Transmission electron microscope (TEM) indicated that the length of the nickel nanotubules were 500–1000 nm with inner diameter 30–150 nm and the thickness of their wall 5–20 nm. The magnetic properties of the nanotubules reached as high as coercivity Hc≈95 Oe.
Keywords: Metal-reduction; Nickel nanotubule; Ethanol amine; Zinc;

A novel metal-organic framework [Zn(bpdc)(DMSO)]·2 DMSO (1) (bpdc=4,4-biphenyldicarboxylate) was prepared by slow vapor diffusion method and characterized by single-crystal X-ray diffraction analysis. In the crystal structure of 1, the square grids [Zn(bpdc)(DMSO)] constructed with paddle-wheel [Zn2(OOC)4] building units and bpdc linkers stack over each other in a ABAB fashion to generate one-dimensional microporous channel that guest DMSO molecules occupy.
Keywords: Metal-organic framework; Paddle-wheel unit; Crystal structure; Guest inclusion;

Under hydrothermal conditions, Tb(NO3)3·5H2O reacted with 3,5-pyridinedicarboxylic acid (3,5-PDCH2) to give a 3-D coordination polymer with the empirical formula of [Tb2 (3,5-PDC)2(H2O)4(C2O4)]·2H2O (1). Tb(NO3)3·5H2O also reacted with 2,4-pyridinedicarboxylic acid (2,4-PDCH2) to give another 3-D coordination polymer [Tb2 (2,4-PDC)2(H2O)2(C2O4)] (2). The structures of both polymers have been determined by X-ray diffraction. X-ray structure analyses show that both polymers contain bridging oxalate (C2O4 2−) ligands, which might have been formed by the reductive coupling of CO2 molecules released from the PDC2− ligands through the C–C bond cleavage.
Keywords: Terbium; Coordination polymers; Carbon dioxide; Oxalate; Reductive coupling;

Synthesis and characterization of dinuclear lanthanide(III) and yttrium(III) cryptates of a hexavalent anionic polydentate ligand by Masatoshi Kanesato; Hirohiko Houjou; Yoshinobu Nagawa; Kazuhisa Hiratani (984-988).
Reaction of tris(2-aminomethyl)amine with bis(hydroxybenzaldehyde) (1) in presence of M(CF3SO3)3 (M=Y, Gd, Tb, Dy, Ho, Er, Tm) in methanol yielded the dinuclear lanthanide(III) and yttrium(III) cryptates [M2L] (2). The structure of [Y2L] was established by X-ray crystallography. Each yttrium ion is in a seven-coordinate environment composed of three imine nitrogen atoms, one apical nitrogen atom, and three oxygen atoms. The dinuclear complexes were found to be a host for Rb+ and Cs+.
Keywords: Lanthanide cryptate; Yttrium cryptate; Dinuclear complex; Crystal structure;

The synthesis and structural characterization of a novel layered compound [Na0.5FeMoH1.5O5] n by De-Qing Chu; Cheng-Ling Pan; Li-Mei Duan; Ji-Qing Xu; Li-Min Wang; Ji-Hui Yu; Tie-Gang Wang (989-992).
Single crystal of [Na0.5FeMoH1.5O5] n has been hydrothermally (160 °C, 72 h, autogeneous pressure) synthesized and characterized by IR, EPR, XPS, elemental analyses and single-crystal structural analysis which reveals the compound consists of host Mo–O–Fe polymeric layers, and guest Na+ cations between the layers.
Keywords: Molybdenum and iron oxide; Crystal structure; Hydrothermal synthesis; Layered;

The closed-shell metalloporphyrins Hf(TPP)(OAc)2 and Th(TPP)(acac)2 (TPP=dianion of tetraphenylporphyrin, OAc=acetate, acac=acetylacetonate) display intraligand fluorescence and additional heavy-atom-induced intraligand phosphorescence, which is observed at room temperature in fluid solution and very efficiently quenched by O2 with potential significance for the sensing of trace amounts of dioxygen.
Keywords: Porphyrins; Hafnium; Thorium; Luminescence; Triplet emitters; Dioxygen sensors;

An aqueous ammonium acetate buffer solution (pH 4) containing vanadate, tungstate and dithionite ions, on heating at 100 °C for 1 h yields one-dimensional polyoxometalate chain compound (NH4)4.68[(VVO4)WVI 8M4O36(VIVO)2]·12H2O (M=0.71VIV+0.29WVI) 1, which is characterized by single-crystal X-ray structure determination, redox titration, and IR spectroscopic studies. Crystallographic data for 1, H42.72N4.68O54V5.84W9.16, tetragonal, space group I   4 ̄ , a=15.8132(5), c=11.1114(5) Å, Z=2, V=2778.5(2) A ̊ 3 .
Keywords: Polyoxometalate; Tungstovanadate heteropoly complex; Reduction; One-dimensional chain;

A novel ladder coordination polymer [CuI 2(ip)(4,4-bipyridine)] · 3.5H2O (1) (ip=isophthalate) was prepared via redox reaction under hydrothermal conditions and characterized by single-crystal X-ray diffraction analysis. In the crystal structure of 1, each ring of the ladder is interlocked by two different, symmetry-related ladders, and the polycatenation of ladders forms a 3D network with rhombic channels clathrating water molecules.
Keywords: Microporous framework; Ladder; Coordination polymer; Crystal structure;

In the presence of the guest molecule, 2,5-bis(3-pyridyl)-1,3,4-oxadiazole (bpo), the title complex {[Cu(bpy)2(H2O)2]·(ClO4)2·(bpo)·3H2O} n (1), was prepared from the reaction of Cu(ClO4)2·6H2O and 4,4-bipyridine (bpy) in CH3CN–H2O mixture. 1 has a 2-D square-grid network structure. The square grids superpose on each other to form a channel framework, in which each layer consists of two pairs of shared edges, almost perfectly square plane with one CuII ion and a bpy at each corner and side, respectively. The square cavity has dimensions of 11.174×11.179  A ̊ . One guest bpo molecule is clathrated in each hydrophobic host cavity and is further stabilized by hydrogen bonding and π–π stacking interactions. The thermogravimetric analysis (TGA) and magnetic properties of complex 1 are also reported.
Keywords: Crystal structure; Inclusion coordination polymer; CuII complex; Host–guest chemistry;

Two oxo-bridged dinuclear ruthenium(III) complexes, [(Py)3(C2O4)RuIIIORuIII(C2O4)(Py)3] (1) and [(4-MePy)3(C2O4)RuIIIORuIII(C2O4)(4-MePy)3]·2-Mebmz ·3H2O (2) (Py = pyridine; 4-MePy = 4-Methylpyridine; 2-Mebmz = 2-methylbenzimidazole) were prepared by reacting RuCl3 with K2C2O4 and pyridine or 4-Methylpyridine and characterized by spectral data and X-ray crystallography. In both (1) and (2), the Ru–O–Ru bonds are linear, with the two C2O4 2− ions trans to each other at the terminal positions. The magnetic susceptibility of (1) was analyzed using a general isotropic exchange Hamiltonian H=−2JS1·S2  (S1=S2=1/2), yielding an antiferro-magnetic spin coupling constant J=−53  cm −1 .
Keywords: Susceptibility study; Crystal structure; Dinuclear ruthenium(III) complex; Linear Ru–O–Ru bond;

First macrocyclic oxamide Cu(II)–Co(II) complex: synthesis, crystal structure and magnetic properties by Jin-Kui Tang; Shu-Feng Si; Li-Ya Wang; Dai-Zheng Liao; Zong-Hui Jiang; Shi-Ping Yan; Peng Cheng; Xin Liu (1012-1015).
A oxamido-bridged binuclear complex, [Cu(L)Co(bpy)2](ClO4)2·0.5C2H5OH·H2O has been synthesized, and structurally and magnetically characterized, where L = 1,4,8,11- tetraazacyclotradecanne-2,3-dione and bpy = 2,2-bipyridine. In the complex, the copper atom from the macrocyclic oxamido-copper(II) precursor in a square-planar and cobalt atoms in a distorted octahedral environment is bridged by the oxamidate group, Cu⋯Co separation of 5.359 Å. The metal–metal separations are consistent with the sequence of decrease of the ion radius of the metal ion. The magnetic properties of the complex have been investigated. The χ M T versus T plots is typical of antiferromagnetically coupled Cu(II)–Co(II).
Keywords: Copper; Macrocyclic oxamide; Magnetic properties; Crystal structure;