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Microreviews

Solution-Processed Chalcopyrites

Direct Liquid Coating of Chalcopyrite Light-Absorbing Layers for Photovoltaic Devices (p NA)
Teodor Todorov, David B. Mitzi
Published Online: Nov 24 2009 1:14AM
DOI: 10.1002/ejic.200900837

	High-throughput deposition techniques available from coating and printing industries can be adapted for photovoltaic manufacturing, replacing costly vacuum processing. Recent advances in directliquid-coating techniques for chalcopyrite thin films have achieved high device efficiencies. Transfer of these techniques to large-volume and low-cost production is in progress.

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Short Communications

Imidobis(phosphaalkene) Complexes

Access to Metal Complexes of the Elusive Imidobis(phosphaalkene) Anion by N-Si Bond Cleavage of a N-Silylimino-Bridged Bis(phosphaalkene) (p NA)
Roxana M. Bîrzoi, Delia Bugnariu, Rafael Guerrero Gimeno, Antje Riecke, Constantin Daniliuc, Peter G. Jones, László Könczöl, Zoltán Benkõ, László Nyulászi, Rainer Bartsch, Wolf-W. du Mont
Published Online: Nov 25 2009 12:47PM
DOI: 10.1002/ejic.200900982

	The [(iPrMe2Si)2C=P]2NSiMe3 (4a) is an excellent precursor for binuclear AuI and RhI complexes of the P,P-coordinated imidobis(phosphaalkene) anion [(iPrMe2Si)2C=P]2N-, the first case of elusive P=C-unsaturated congeners of the classic bis(phosphanyl)amide ligands.

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Perfluorophosphanes

2,3,5,6-Tetrafluoro-p-phenylenebis(phosphanes) - Preparation and Structure of an Electron-Poor P-R_F-P Linker (p NA)
Andreas Orthaber, Ferdinand Belaj, Jörg H. Albering, Rudolf Pietschnig
Published Online: Nov 24 2009 10:46AM
DOI: 10.1002/ejic.200901042

	1,4-Bis[bis(diethylamino)phosphanyl]-2,3,5,6-tetrafluorobenzene and 1,4-bis(dichlorophosphanyl)-2,3,5,6-tetrafluorobenzenehave been synthesized in good yields and structurally characterized, now opening the way to the synthesis of low-coordinatedbis(phosphanes) linked by an electron-deficient aryl moiety.

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A Cu/Co/Ni Pentanuclear Core

A Pentanuclear Cu/Co/Ni Complex with 2-(Dimethylamino)ethanol - Observation of a Rare Molecular Structure Type and Its Place in General Structural Types: An Analysis of the Cambridge Structural Database (p NA)
Dmytro S. Nesterov, Vladimir N. Kokozay, Brian W. Skelton
Published Online: Nov 18 2009 8:56AM
DOI: 10.1002/ejic.200900815

	The heterotrimetallic Cu/Co/Ni complex with 2-(dimethylamino)ethanol has been prepared by direct synthesis. The pentanuclear coordination core of the presented complex possesses extremely rare asymmetric organization. The general pentanuclear molecular structure types and their comparison with the structure of the presented compound are discussed.

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Hierarchical Microspheres

Tartatric Acid and L-Cysteine Synergistic-Assisted Synthesis of Antimony Trisulfide Hierarchical Structures in Aqueous Solution (p NA)
Jun Pan, Shenglin Xiong, Baojuan Xi, Jiangfa Li, Jiangying Li, Hongyang Zhou, Yitai Qian
Published Online: Nov 11 2009 10:58AM
DOI: 10.1002/ejic.200900607

	Hierarchical Sb2S3 microspheres with alveolate-like structures were successfully prepared through a hydrothermal method without the use of a surfactant in aqueoussolution. Results reveal that L-cysteine and tartatric acid play a key role in the morphology of the Sb2S3 products.

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Titanium Complexes

Structural Consequences in - and -Glucopyranosidato Complexes of Cp*TiCl₃ (p NA)
Dirk Schwidom, Daniela Zeysing, Michael Schmidt, Jürgen Heck
Published Online: Nov 3 2009 1:04PM
DOI: 10.1002/ejic.200900753

	The change of the configuration at only one carbon atom of the monosaccharide ligand induces a change of the absolute configuration of the metal centre of the corresponding titanium complexes. The configurational change is easily seen by a projection of the molecular structure along the molecular C2 axis: The S shape of 1 changes into an overall inverse S shape of 2.

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Sol-Gel Synthesis

Aluminum Alkoxide Fluorides Involved in the Sol-Gel Synthesis of Nanoscopic AlF₃ (p NA)
Anton Dimitrov, Julia Koch, Sergey I. Troyanov, Erhard Kemnitz
Published Online: Oct 23 2009 11:45AM
DOI: 10.1002/ejic.200900774

	Three aluminum alkoxide fluorides as intermediates of the fluorolysis of aluminum isopropoxide with HF in pyridine have been isolated and structurally characterized [see structure of Al7F10(4-O)(O-Pr)9(Py)3; yellow Al, green F, red O, blue N, gray C]. These compounds represent possible snapshots in the consecutive fluorolytic sol-gel formation of nanoscopic AlF3.

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Full Papers

Silyl-Substituted Bismuthanes

Reduction vs. Metathesis in the Reactions of Bismuth Tribromide with a Bulky Lithium Silanide - An Experimental and Theoretical Study (p NA)
Kirill Yu. Monakhov, Thomas Zessin, Gerald Linti
Published Online: Nov 27 2009 12:00PM
DOI: 10.1002/ejic.200900773

	The very stable silyl-substituted dibismuthane is the result of redox conversions via metathesis reactions of bismuth halideBiBr3 with silyllithium tBuPh2SiLi(thf)3 in various ratios.

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Radical Substitution

A Radical Approach to Hydroxylaminotrichlorosilanes: Synthesis, Reactivity, and Crystal Structure of TEMPO-SiCl₃ (TEMPO = 2,2,6,6-Tetramethylpiperidine-N-oxyl) (p NA)
Spirk Stefan, Ferdinand Belaj, Tobias Madl, Rudolf Pietschnig
Published Online: Nov 26 2009 11:49AM
DOI: 10.1002/ejic.200900969

	The radical TEMPO reacts with SiCl4 with formation of the primary substitution product TEMPO-SiCl3 besides several chlorinated and protonated TEMPO derivatives. This set of closely related compounds has been characterized by X-raycrystallography and spectroscopic techniques (IR, NMR). DFT calculations [B3LYP//6-311+G(d)] have been carried out to understand the driving force behind their formation.

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In-situ Ligand Synthesis

Nucleophilic Addition of Water and Alcohols to Dicyanonitrosomethanide: Ligands with Diverse Bonding Modes in Magnetically Coupled d-Block Complexes (p NA)
Anthony S. R. Chesman, David R. Turner, Boujemaa Moubaraki, Keith S. Murray, Glen B. Deacon, Stuart R. Batten
Published Online: Nov 26 2009 11:49AM
DOI: 10.1002/ejic.200900779

	The addition of an alcohol to dicyanonitrosomethanide results in derivative ligands, which have been utilised in the formation of a series of discrete complexes and 1D and 2D coordination polymers. The coordination modes of the ligands often show novel features and the magnetic properties of the resultant products were investigated.

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Hemilabile Phosphane Ligands

Preparation, Crystal Structures, and Spectroscopic and Redox Properties of Nickel(II) Complexes Containing Phosphane-(Amine or Quinoline)-Type Hybrid Ligands and a Nickel(I) Complex Bearing 8-(Diphenylphosphanyl)quinoline (p NA)
Akira Hashimoto, Hiroshi Yamaguchi, Takayoshi Suzuki, Kazuo Kashiwabara, Masaaki Kojima, Hideo D. Takagi
Published Online: Nov 26 2009 11:49AM
DOI: 10.1002/ejic.200900767

	The coordination geometry of nickel(II) complexes with (2-aminoethyl)phosphanes, cis(P,P)-[Ni(RRPea)2](BF4)2 (RR = Ph2 or MePh) is square planar in the solid state and in solution, whereas the correspondingcomplexes with 8-quinolylphosphanes, cis(P,P)-[Ni(RRPqn)2](BF4)2, exhibit a tetrahedral distortion in their coordination planes, which results in weaker ligand-field strengths for RRPqn than for RRPea.

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Coated Conductors

CeO₂ Buffer Layers for HTSC by an Aqueous Sol-Gel Method - Chemistry and Microstructure (p NA)
Nigel Van de Velde, David Van de Vyver, Oliver Brunkahl, Serge Hoste, Els Bruneel, Isabel Van Driessche
Published Online: Nov 26 2009 11:49AM
DOI: 10.1002/ejic.200900257

	CeO2 thin films were synthesized on both NiW and La2Zr2O7-buffered NiW by a novel, aqueous citric acid based chemical solution deposition (CSD) method. Sufficient thickness was achieved in combination with good texture. The introduction of doping elements allowed us to synthesize dense materials with good morphology.

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Osmium Tetraphosphorus Complexes

Synthesis, Characterization and Hydrolysis of Osmium Tetraphosphorus Complexes (p NA)
Maria Caporali, Massimo Di Vaira, Maurizio Peruzzini, Stefano Seniori Costantini, Piero Stoppioni, Fabrizio Zanobini
Published Online: Nov 25 2009 12:47PM
DOI: 10.1002/ejic.200900884

	The monometallic complex [CpOs(PPh3)2(1-P4)]OTf, in which the tetrahedral white phosphorus P4 molecule is 1 bound to the CpOs(PPh3)2 metal fragment, and theheterobimetallic [{CpRu(PPh3)2}{CpOs(PPh3)2}(,1:1-P4)](OTf)2 compound (see graphic), in which the tetrahedral P4 tethers two different metal fragments via two phosphorus atoms, have been synthesized and characterized.

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Dendritic Metal Complexes

Fréchet-Type Pallado-Dendrimers Containing Bis(pyrazolyl)methane Ligands (p NA)
Alberto Sánchez-Méndez, Ernesto de Jesús, Juan C. Flores, Pilar Gómez-Sal
Published Online: Nov 25 2009 12:47PM
DOI: 10.1002/ejic.200900869

	Discrete and dendritic (scorpionato)PdII complexes have been synthesized and evaluated as catalyst precursors in the Heck reaction. The active catalytic species formed from these precursors are apparently not coordinated to the bis(pyrazolyl)methane ligands.

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C-H Bond Activation

Intramolecular C-H Bond Activation by Lanthanoid Complexes Bearing a Bulky Aminopyridinato Ligand (p NA)
Sadaf Qayyum, Grigorii G. Skvortsov, Georgii K. Fukin, Alexander A. Trifonov, Winfried P. Kretschmer, Christian Döring, Rhett Kempe
Published Online: Nov 24 2009 10:46AM
DOI: 10.1002/ejic.200900723

	Bisaminopyridinate lanthanoid alkyl complexes may undergo intramolecular methyl group C-H activation. The larger the lanthanide the faster is the decomposition of its parent. In consequence, stable alkyls can only be isolated for the late lanthanoids. Converting them into transient hydrides gives rise to C-H activation products as well.

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Neutral Pd Metallocycle as Precatalyst

Neutral Trinuclear Palladium(II) Metallocycles with Mixed Phosphane/Pyridine-4-thiolato Ligands and Their Catalytic Tests in Suzuki-Miyaura Coupling Reactions (p NA)
Hui Wang, Rui Zhong, Xu-Qing Guo, Xiao-Yan Feng, Xiu-Feng Hou
Published Online: Nov 24 2009 1:14AM
DOI: 10.1002/ejic.200900895

	Three neutral trinuclear palladium(II) complexes with mixed phosphane and pyridine-4-thiolato ligands were self-assembled from the corresponding metal fragments [R3PPdCl2]2 with lithium pyridine-4-thiolate (PySLi). A preliminary study on the Suzuki-Miyaura coupling shows that the novel trinuclear PdII complexes with a PyS bridge are more active precatalysts than [R3PPdCl2]2 complexes.

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Inkjet Printing

Inkjet Printing of Water Soluble Doped ZnS Quantum Dots (p NA)
Aaron C. Small, James H. Johnston, Noel Clark
Published Online: Nov 24 2009 1:14AM
DOI: 10.1002/ejic.200900871

	Doped ZnS quantum dots were synthesised and subsequently inkjet-printed onto a variety of substrates including inkjet-quality photographic paper, cotton, merino wool, PET film, PEDOT-coated PET film, and silicon wafer. The most successful were inkjet-quality photographic paper and cotton, on which complicated patterns were printed that gave rise to photoluminescence.

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Copper(I)/(II) Complexes

Copper-Azide-Thioarylazoimidazoles - Structure, Spectra, Redox Properties, Magnetism and Theoretical Interpretation (p NA)
Prasenjit Bhunia, Debasis Banerjee, Papia Datta, Pallepogu. Raghavaiah, Alexandra M. Z. Slawin, John D. Woollins, Joan Ribas, Chittaranjan Sinha
Published Online: Nov 24 2009 1:14AM
DOI: 10.1002/ejic.200900648

	Tetranuclear azido-bridged copper(II) and binuclear methanol-bridged copper(I) complexes of 1-alkyl-2-[(o-thioalkyl)phenylazo]imidazole (SRaaiNR) are interconvertible: CuII is reduced by ascorbic acid, while CuIcomplexes are oxidised by chlorine/water in the presence of an excess amount of NaN3. The tetranuclear CuII complex shows ferromagnetic and antiferromagnetic interactions.

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Nanoscale Photomagnetism

Light-Induced Stored Information in Nanoparticles (p NA)
Suzanne M. Neville, Céline Etrillard, Saket Asthana, Jean-François Létard
Published Online: Nov 20 2009 9:19AM
DOI: 10.1002/ejic.200900937

	We use reverse micelle techniques to prepare microscale and nanoscale (30-80 nm) particles of the spin-crossover coordination polymer [Fe(NCS)2(bpe)2]. By comparing the thermal and photoinduced magnetic behaviours of these and that of the original slow-grown macroscale crystals, we show that with particle size reduction, even to the nanoscale, the photoinduced magnetic properties are retained.

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Microporous Titanosilicates

Exfoliated Titanosilicate Material UZAR-S1 Obtained from JDF-L1 (p NA)
César Rubio, Clara Casado, Patricia Gorgojo, Fernando Etayo, Santiago Uriel, Carlos Téllez, Joaquín Coronas
Published Online: Nov 20 2009 9:19AM
DOI: 10.1002/ejic.200900915

	UZAR-S1 has been obtained by exfoliation of the layered precursor microporous titanosilicate JDF-L1. The dispersion of this material in commercial polysulfone results in an improved H2-selective mixed matrix membrane.

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Palladium(II)/Platinum(II) Complexes

Solvent Effects on Coordination Chemistry - Stepwise Synthesis and Structural Properties of Monometallic Palladium(II) Complexes and Bimetallic Palladium(II)/Platinum(II) Complexes (p NA)
Tae Hwan Noh, Young-A Lee, Ok-Sang Jung
Published Online: Nov 20 2009 9:19AM
DOI: 10.1002/ejic.200900804

	Stepwise syntheses of monometallic palladium(II) and bimetallic palladium(II)/platinum(II) complexes containing a series of potential tetradentate (O,O,S,S) ligands were carried out. PdII favored the O,O-chelate whereas PtII favored theS,S-chelate in the solid state. Notably different solution behavior due to the steric hindrance between the palladium square plane and the ylidene moiety were observed.

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Binuclear Metal Complexes

Syntheses of the First Coordination Compounds of the New Strong Molecular Electron Donor and Double Proton Sponge 1,4,5,8-Tetrakis(tetramethylguanidino)naphthalene (p NA)
Viktoriia Vitske, Carolin König, Olaf Hübner, Elisabeth Kaifer, Hans-Jörg Himmel
Published Online: Nov 20 2009 9:19AM
DOI: 10.1002/ejic.200900724

	Binuclear coordination compounds with an unusual geometry can be synthesised with the new superbasic tetraguanidino ligand 1,4,5,8-tetrakis(tetramethylguanidino)naphthalene. The consequences on magnetic exchange is analysed for the example of a bincuclear CoII complex.

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Bioorganometallic Chemistry

C₂-Symmetric Ferrocene-Bis(ureido)peptides: Synthesis, Conformation and Solid-State Structure (p NA)
Jasmina Lapi, Senka Djakovi, Mario Cetina, Katja Heinze, Vladimir Rapi
Published Online: Nov 20 2009 9:19AM
DOI: 10.1002/ejic.200900679

	Formal NH insertion in peptidic bioconjugates of ferrocene-1,1-dicarboxylic acidresults in ferrocene-bis(ureido)peptides. Conformational analyses were performed by IR, NMR and CD spectroscopy and augmented by DFT calculations. A stable intramolecular hydrogen-bond pattern with double bifurcated intramolecular hydrogen bonds is revealed.

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Bis(phosphoranido) Complexes

Syntheses and Characterization of Novel trans-Bis(phosphoranido)platinum(II) Complexes: Reactions of Lithium Bis(naphth-1,8-diyl-8-oxy)phosphoranide with cis-PtCl₂(PR₃)₂ (R = OPh, OMe, Me) (p NA)
Kazumasa Kajiyama, Issei Sato, Satoru Yamashita, Takeshi K. Miyamoto
Published Online: Nov 17 2009 11:04AM
DOI: 10.1002/ejic.200900834

	trans-Bis(phosphoranido)platinum(II) complexes, which are the first square-planar complexes to bear two phosphoranide ligands in a trans array, were synthesized. The structural property was confirmed by X-ray structural analysis of the bis(phosphoranido) complex bearing triphenyl phosphites.

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Tuning Supramolecular Networks

Change in Supramolecular Networks through In Situ Esterification of Porphyrins (p NA)
Wentong Chen, Shunichi Fukuzumi
Published Online: Nov 17 2009 1:03AM
DOI: 10.1002/ejic.200900801

	Eight esterified TCPP compounds were successfully synthesized by solvothermal reactions and characterized. The reaction mechanism was investigated. Esterification plays a vital role in the properties, structural motifs and supramolecular networks.

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Spin Crossover

On the Spin Behaviour of Iron(II)-Dipyridyltriazine Complexes and Their Performance as Thermal and Photonic Spin Switches (p NA)
Sophie K. Hain, Frank W. Heinemann, Klaus Gieb, Paul Müller, Gerald Hörner, Andreas Grohmann
Published Online: Nov 17 2009 1:03AM
DOI: 10.1002/ejic.200900588

	Three de novo synthesized iron(II) complexes show markedly diverging thermal and photonic spin behaviour in solution. The substantial thermochromism of the complexes in DMSO is due to a competition between ligand substitution and a thermally induced spin crossover. Efficient photonic low-spin to high-spin switching prevails even in strongly coordinating solvents.

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Nickelacyclic Carboxylates

Nickelacyclic Carboxylates with Pyridine-Based Ligand Sets - From Mononuclear Complexes to Supramolecular Architectures by Hydrogen Bonding (p NA)
Jens Langer, Dirk Walther, Astrid Malassa, Matthias Westerhausen, Helmar Görls
Published Online: Nov 13 2009 11:51AM
DOI: 10.1002/ejic.200900888

	The synthesis, characterization and self-assembly via hydrogen bonding of nickelacyclic carboxylates bearing substituted pyridine ligands is reported.

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Chiral (Olefin)amine Ligands

Chiral [Bis(olefin)amine]rhodium(I) Complexes - Transfer Hydrogenation in Ethanol (p NA)
Theo Zweifel, David Scheschkewitz, Timo Ott, Matthias Vogt, Hansjörg Grützmacher
Published Online: Nov 13 2009 11:51AM
DOI: 10.1002/ejic.200900875

	A number of chiral [bis(olefin)amino]rhodium(I) complexes containing a tropylidenyl moiety (blue) were synthesized and tested in enantioselective transfer hydrogenations by using ethanol as green hydrogen donor. The best results were obtained with a ligand containing a cyclohex-3-en-1-yl group (red) (up to 44 % ee at a substrate/catalyst ratio S/C = 10000).

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Boron Clusters

hypercloso-Hexa(amino)hexaboranes: Structurally Related to Known hypercloso-Dodecaboranes, Metastable with Regard to Their Classical Cycloisomers (p NA)
Wahid Mesbah, Meisam Soleimani, Elham Kianfar, Gertraud Geiseler, Werner Massa, Matthias Hofmann, Armin Berndt
Published Online: Nov 13 2009 11:51AM
DOI: 10.1002/ejic.200900850

	In spite of their weak aromaticity and in contrast to reports in the literature, hypercloso-hexa(amino)hexaboranes like A are higher in energy than the corresponding cycloisomers like B. This is shown experimentally as well as by computations at the B3LYP/6-311+G** level of theory. Compound A is the first hypercloso-hexaborane to be characterized by X-ray structural analysis.

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Chiral Phospholenes

Enantiomerically Pure P,N Chelates Based on Phospholene Rings: Palladium Complexes and Catalytic Applications in Allylic Substitution (p NA)
François Leca, Fernando Fernández, Guillermo Muller, Christophe Lescop, Régis Réau, Montserrat Gómez
Published Online: Nov 11 2009 10:58AM
DOI: 10.1002/ejic.200900892

	The synthesis of optically pure 2-pyridylphospholene ligands by diastereomeric resolution of PdII complexes also bearing the chiral amine (R)--methylbenzylamine is described. A full coordination study ofthese ligands and the corresponding phosphole ligands has been carried out. Their catalytic behaviour in Pd-catalysed allylic substitutions has also been evaluated.

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Germanium Nanomaterials

Synthesis and Characterization of Germanium Coordination Compounds for Production of Germanium Nanomaterials (p NA)
Timothy J. Boyle, Louis J. Tribby, Leigh Anna M. Ottley, Sang M. Han
Published Online: Nov 9 2009 11:18AM
DOI: 10.1002/ejic.200900556

	A series of GeII precursors-Ge[OC6H3(C6H5)2]2 shown-were synthesized for production of Ge0 nanomaterials. Upon precipitation from solution, it was found that Ge0 nanodots were formed from the amide, nanowires from alkoxides (shown) and siloxides, and amorphous GexSy from the silanthiolate.

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Electrocatalysis

Electrooxidation of Fe, Co, Ni and Cu Metalloporphyrins on Edge-Plane Pyrolytic Graphite Electrodes and Their Electrocatalytic Ability towards the Reduction of Molecular Oxygen in Acidic Media (p NA)
Gregory Richards, Shawn Swavey
Published Online: Nov 6 2009 8:36AM
DOI: 10.1002/ejic.200900651

	Electrooxidation of FeIII, CoII, NiII and CuII porphyrins onto graphite electrodes creates an electroactive surface capable of catalyzing the reduction of oxygen in acidic media.

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Alkyne Cyclotrimerization on W

Inhibition of Alkyne Cyclotrimerization to Arenes on a Metal Site by Four-Electron Donation through Simultaneous Sigma and Pi Bonding: The Tris(alkyne)Tungsten Carbonyls (p NA)
Bin Peng, Qian-Shu Li, Yaoming Xie, R. Bruce King, Henry F. Schaefer III
Published Online: Nov 5 2009 11:07AM
DOI: 10.1002/ejic.200900827

	The isomerizations of (RCCR)3W(CO)n (n = 3, 2) to (6-C6R6)W(CO)n are predicted by density functional theory to be very exothermic. However, the isomerizations of (RCCR)3W(CO) and (RCCR)3W to (6-C6R6)W(CO) and (6-C6R6)W, respectively, are predicted to be nearly thermoneutral (R = CH3) to highly endothermic (R = CF3).

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Biomimetic Chemistry

Synthesis, Characterization, and Oxygenation Studies of Carboxylate-Bridged Diiron(II) Complexes with Aromatic Substrates Tethered to Pyridine Ligands and the Formation of a Unique Trinuclear Complex (p NA)
Simone Friedle, Stephen J. Lippard
Published Online: Nov 5 2009 11:07AM
DOI: 10.1002/ejic.200900821

	Carboxylate-rich diiron compounds are prepared with tethered aromatic substrates as structural and functional models for the active sites of non-heme diiron metalloproteins.

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Coordination Versatility in Supramolecules

Structure and Properties of Copper(II), Manganese(III), and Iron(III) Complexes with Potentially Pentaanionic Heptadentate Ligands Including Alkoxido, Amido, and Phenoxido Donors (p NA)
Liliana Stoicescu, Carine Duhayon, Laure Vendier, Ana Tesouro-Vallina, Jean-Pierre Costes, Jean-Pierre Tuchagues
Published Online: Nov 5 2009 11:07AM
DOI: 10.1002/ejic.200900791

	The coordination ability and versatility of the potentially pentaanionic heptadentate ligands H5L1-H5L3 towards transition-metal ions is demonstrated by the different dinucleating chelation modes described in this report. The sheetlike packing in the 2D [Cu2(L1)(OAc)Cs2(MeOH)2]n coordination polymer is shown.

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(Hydrido)Osmium Complexes

Hydrido-Osmium(II), -Osmium(IV) and -Osmium(VI) Complexes with Functionalized Phosphanes as Ligands (p NA)
Birgit Richter, Helmut Werner
Published Online: Nov 5 2009 11:07AM
DOI: 10.1002/ejic.200900706

	Hexahydrido-Os(VI) phosphane complexes can be prepared from Os(IV) precursors of type A and were shown to rapidly react with O2 and primary alcohols. Their catalytic hydrogen transfer activity was briefly investigated.

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Metal-Promoted Cycloadditions

Platinum(II)-Promoted [2+3] Cycloaddition of Azide with 4-Cyanobenzaldehyde, a Schiff Base Derivative or Dicyanobenzenes To Give Formyl-, Amino(imino)- or Cyano-Functionalized Tetrazolato Complexes (p NA)
Jamal Lasri, M. Fátima C. Guedes da Silva, Maximilian N. Kopylovich, Bhaswati Ghosh Mukhopadhyay, Armando J. L. Pombeiro
Published Online: Nov 4 2009 9:44AM
DOI: 10.1002/ejic.200900858

	Cycloaddition of bis(azido)platinum(II) with 4-cyanobenzaldehyde furnishes (formylphenyl)tetrazolate PtII that reacts with 2-dimethylaminoethylamine to give the corresponding Schiff base derivative; the latter undergoes hydrolysis in the presence of a metal salt. Reactions with dicyanobenzenes give (cyanophenyl)tetrazolate complexes.

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Trinucelar Complexes

Control of Exchange Interactions in Trinuclear Complexes Based on Orthogonal Magnetic Orbitals (p NA)
Birgit Weber, Jaroslava Obel, Lucia R. Lorenz, Wolfgang Bauer, Luca Carrella, Eva Rentschler
Published Online: Nov 4 2009 9:44AM
DOI: 10.1002/ejic.200900847

	The magnetic properties of trinuclear complexes can be controlled by using the principles of strict orthogonality of the magnetic orbitals.

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Spin-Crossover Complexes

Two New Iron(II) Spin-Crossover Complexes with N₄O₂ Coordination Sphere and Spin Transition around Room Temperature (p NA)
Birgit Weber, Jaroslava Obel, Dunie Henner-Vásquez, Wolfgang Bauer
Published Online: Nov 4 2009 9:44AM
DOI: 10.1002/ejic.200900846

	A new modification of an N2O2 coordinating Schiff base like ligand enables a more detailed investigation of the influence of H-bonds on spin-crossover properties. A significant increase in the transition temperature was observed.

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Hydroxyapatite Hollow Spheres

Solvothermal Synthesis and Characterization of Hierarchically Nanostructured Hydroxyapatite Hollow Spheres (p NA)
Ming-Guo Ma, Jie-Fang Zhu
Published Online: Nov 4 2009 9:44AM
DOI: 10.1002/ejic.200900839

	The solvothermal synthesis of hierarchically nanostructured hydroxyapatite hollow spheres assembled from nanorods was carried out at 200 °C for 24 h in water/N,N-dimethylformamide (DMF) mixed solvents.

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Bioorganometallic Chemistry

Tricarbonylmanganese(I) and -rhenium(I) Complexes of Imidazol-Based Phosphane Ligands: Influence of the Substitution Pattern on the CO Release Properties (p NA)
Peter C. Kunz, Wilhelm Huber, Alfonso Rojas, Ulrich Schatzschneider, Bernhard Spingler
Published Online: Nov 4 2009 9:44AM
DOI: 10.1002/ejic.200900650

	MnI- and ReI(CO)3 complexes of imidazolyl-based phosphane ligands were prepared. The Mn(CO)3 complexes were studied as CO-releasing molecules (CORMs). Within the series of compounds prepared, the substitution pattern of the imidazolyl groups was found to significantly influence the CO release efficiency and stoichiometry.

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Stable Metal-Organic Frameworks

Sulfonic Acid Analogs of Terephthalic and Trimesic Acid as Linkers in Metal-Organic Frameworks - Synthesis of Thermally Robust MOFs (p NA)
Andrea Mietrach, Thomas W. T. Muesmann, Jens Christoffers, Mathias S. Wickleder
Published Online: Oct 29 2009 9:46AM
DOI: 10.1002/ejic.200900914

	Acidity brings stability: Thermal stability of over 400 °C is achieved for metal-organic frameworks, if copper(II) is linked by 1,4-benzenedisulfonate or 1,3,5-benzenetrisulfonate. The respective sulfonic acids with appropriate substitution pattern are prepared in an efficient and scalable two-step protocol from bromobenzene derivatives.

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Tris(pyrazolyl)borate Ligands

para-Bromophenyl[tris(pyrazolyl)]borate Complexes of Group 1 Metals, Thallium and Magnesium: Synthesis and Characterization of Transfer Agents for Third-Generation Tp Ligands (p NA)
Johannes Zagermann, Matthew C. Kuchta, Klaus Merz, Nils Metzler-Nolte
Published Online: Oct 29 2009 9:46AM
DOI: 10.1002/ejic.200900707

	A series of third-generation tris(pyrazolyl)borate (Tp) transfer agents p-BrC6H4TpM (M = Na, K, Rb, Cs, Tl), p-BrC6H4Tp*Tl, (p-BrC6H4Tp)2Mg, p-BrC6H4TpMeK and p-BrC6H4Tp*K was synthesized and characterized. Monovalent p-BrC6H4Tp*Tl and the magnesium-sandwich compound (p-BrC6H4Tp)2Mg were structurally characterized in the solid state by X-ray diffraction.

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Mixed-Valent Vanadium Complexes

Divanadium(V) and Trapped Valence Linear Tetravanadium(IV,V,V,IV) Complexes (p NA)
Anindita Sarkar, Samudranil Pal
Published Online: Oct 29 2009 9:46AM
DOI: 10.1002/ejic.200900680

	Divanadium(V) complexes, [(hc)O2V(-diah)VO2(hc)] {hc, N-coordinating neutral heterocycles and H2diah, N,N-bis(diacetyl)hydrazine}, and linear tetravanadium(IV,V,V,IV) complexes, [(acac)2OV(-O)VO(hc)(-diah)(hc)OV(-O)VO(acac)2] (acac, acetylacetonate), are described. The mixed-valence fragments in the tetravanadium species are unsymmetrical and they have a valence localized electronic structure.

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Dinuclear Oxidovanadium Complexes

Dinuclear Oxidovanadium(IV) and Dioxidovanadium(V) Complexes of <br/>5,5-Methylenebis(dibasic tridentate) Ligands: Synthesis, Spectral Characterisation, Reactivity, and Catalytic and Antiamoebic Activities (p NA)
Mannar R. Maurya, Aftab Alam Khan, Amir Azam, Amit Kumar, Samir Ranjan, Neelima Mondal, J. Costa Pessoa
Published Online: Oct 29 2009 9:46AM
DOI: 10.1002/ejic.200900677

	Dinuclear VIVO (1 and 2) and VVO2 (3, 4 and 5) complexes of CH2(H2sal-nah)2 (I) and CH2(H2sal-inh)2 (II) have been synthesised, and their catalytic activities have been studied. Dioxidovanadium(V) complexes have also been screened against HM1:1MSS strains of Entamoeba histolytica.

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Trinuclear Ni(III) Complexes

Ferromagnetic Properties of a Trinuclear Nickel(II) Complex with a Trithiocyanurate Bridge (p NA)
Pavel Kopel, Jerzy Mrozinski, Karel Doleal, Vratislav Langer, Roman Boa, Alina Bieko, Andrzej Pochaba
Published Online: Oct 29 2009 9:46AM
DOI: 10.1002/ejic.200900617

	The trinuclear nickel(II) complex [Ni3(pmdien)3(-ttc)](ClO4)3 with N,N,N,N,N-pentamethyldiethylenetriamine(pmdien) and a trithiocyanurate(3-) (ttc3-) bridge was synthesized. This trinuclear nickel(II) complex has a regular triangular Ni3 core. The trimer showed ferromagnetic interactions among the NiII magnetic centers and spin-glass properties. Biological studies were also investigated.

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Silver Nanofibres

Silver Nanofibres by a Novel Electrospinning Process: Nanofibres with Plasmon Resonance in the IR Region and Thermal Hysteresis Electrical Conductivity Features (p NA)
Nasser A. M. Barakat, Taha E. Farrag, Muzafar A. Kanjwal, Soo-Jin Park, Faheem A. Sheikh, Hak Yong Kim
Published Online: Oct 29 2009 9:46AM
DOI: 10.1002/ejic.200900453

	Electrospinning of a colloidal silver acetate solution rather than the conventional sol-gel process was introduced as a novel strategy to produce silver nanofibres. Electrophoretic light scattering and dynamic light scattering analyses have affirmed that theelectrospun solution is a colloid. Calcination of the electrospun mats produced smooth and unbroken pure silver nanofibres. The advantageous physical features of the fibres suggest utilising the prepared nanofibres in various fields.

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Chiral Dithiolene Complexes

Chiral, Neutral, and Paramagnetic Gold Dithiolene Complexes Derived from Camphorquinone (p NA)
Romain Perochon, Cyril Poriel, Olivier Jeannin, Lidia Piekara-Sady, Marc Fourmigué
Published Online: Oct 28 2009 12:55PM
DOI: 10.1002/ejic.200900855

	Camphor and gold combined into paramagnetic and chiral dithiolene complexes: From camphorquinone, the electron-rich D- or dl-bornylenedithiolato ligands afford the enantiopure [(D-bordt)2Au]· or diastereomeric [(dl-bordt)2Au]· radical complexes as highly soluble paramagnetic crystalline materials.

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Iron Coordination Chemistry

Unsupported -Oxo- and -Hydroxo-Iron(III) Dimers and Mononuclear Iron(III) Complexes with Pyridylbis(aminophenol) Ligands (p NA)
Rajendra Shakya, Douglas R. Powell, Robert P. Houser
Published Online: Oct 28 2009 12:55PM
DOI: 10.1002/ejic.200900794

	Unsupported hydroxo- and oxo-bridged diiron(III) complexes, and monomeric iron(III) complexes were synthesized with with pyridylbis(aminophenol) ligands. The oxo-bridged diiron(III) complex could be protonated to generate its hydroxo-bridged analog, but the hydroxo-bridged dimer could not be deprotonated to generate its oxo-bridged dimer.

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Metal Carbamates

Synthesis and Characterisation of a New Cu(O₂CNAllyl₂)₂ Carbamato Complex and an Unusual Polymeric Cu^I Complex [Cu^I₄Cl₄(NHAllyl₂)₄]_n: New Insights into Metal Carbamato Chemistry (p NA)
Alberto Albinati, Massimo L. Carraro, Silvia Gross, Marzio Rancan, Silvia Rizzato, Eugenio Tondello, Alfonso Venzo
Published Online: Oct 28 2009 12:55PM
DOI: 10.1002/ejic.200900620

	The synthesis of the N,N-diallylcarbamato complex Cu(O2CNAllyl2)2 led to the formation of a polymeric CuI complex [CuI4Cl4(NHAllyl2)4]n. Surprisingly, the reduction of CuII to CuI is coupled to the oxidation of diallylamine to 3,4-dimethylpyrrole.

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Isocyanocarbazole Complexes

Synthesis and Characterization of Gold(I) Complexes with 9-(4-Isocyanophenyl)carbazole or 9-Ethyl-3-isocyanocarbazole Ligands (p NA)
Rut Benavente, Pablo Espinet, Sergio Lentijo, Jose M. Martín-Álvarez, Jesús A. Miguel, M. Paz Rodríguez-Medina
Published Online: Oct 26 2009 4:48AM
DOI: 10.1002/ejic.200900692

	Gold(I) complexes with isocyanocarbazole ligands were prepared. The gold complexes display a redshift in the emissions relative to that of the free ligand. The presence of electron-withdrawing substituents in 3,6-dibromo-9-(4-isocyanophenyl)carbazole quenches the luminescence, but with the introduction of a gold atom some luminescence is recovered.

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Pd-Catalyzed Allylation

Diethylzinc-Mediated Allylation of Carbonyl Compounds Catalyzed by [(NHC)(PR₃)PdX₂] and [(NHC)Pd(³-allyl)Cl] Complexes (p NA)
Alexandre Flahaut, Krimo Toutah, Pierre Mangeney, Sylvain Roland
Published Online: Oct 23 2009 11:45AM
DOI: 10.1002/ejic.200900891

	[(NHC)(PR3)PdX2] complexes are active precatalysts in the Pd-catalyzed allylation of carbonyl compounds with allylic acetates and diethylzinc. The scope of the reaction was investigated with various carbonyl compounds and allylic acetates. An experimental study concerning the mechanism of the reaction was carried out with [(NHC)Pd(3-allyl)Cl] complexes.

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Metal-Cyanoguanidine Complexes

Preparation of Cyanoguanidine and Ethylcyanamide Complexes of Ruthenium(II) and Osmium(II) (p NA)
Gabriele Albertin, Stefano Antoniutti, Jesús Castro
Published Online: Oct 23 2009 11:45AM
DOI: 10.1002/ejic.200900639

	The preparation of cyanoguanidine and diethylcyanamide complexes of ruthenium and osmium, stabilised by the p-cymene fragment [MCl(6-p-cymene)(PR3)], is described. The spectroscopic and crystallographic characterisation of these complexes is also discussed.

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Hybrid Inorganic-Organic Networks

Syntheses, X-ray Diffraction Study and Characterisations of Ni and Zn Complexes of Clodronic Acid and Its Dibenzoyl Derivative (p NA)
Susan Kunnas-Hiltunen, Matti Haukka, Jouko Vepsäläinen, Markku Ahlgrén
Published Online: Oct 23 2009 11:45AM
DOI: 10.1002/ejic.200900500

	Isomorphous Ni and Zn complexes of the dibenzoyl derivative of clodronic acid, 1 and 2, and the isostructural corresponding complexes of clodronic acid, 3 and 4, were prepared and characterized. The coordination polymers 1 and 2 form, through intermolecular hydrogen bonds, dense 2D structures, whereas the monomeric compounds 3 and 4 form a 3D hydrogen-bonded network with solvent-accessiblevoids.

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Dual-Modality Imaging

Pyrene-Functionalised Copper Complexes as Potential Dual-Modality Imaging Agents (p NA)
Jason P. Holland, Victoria Fisher, Jennie A. Hickin, Josephine M. Peach
Published Online: Oct 21 2009 1:13PM
DOI: 10.1002/ejic.200900823

	Pyrene-functionalised copper and zinc complexes of bis(thiosemicarbazonato) ligands have been characterised as potential dual-modality imaging agents for in vitro fluorescence microscopy and in vivo positron emission tomography.

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Three Is the Magic Number

Formation of Unusual Trinuclear Assemblies: Scope and Mechanism of Zn(salphen)-Templated Activation of Pyridine-Alcohol Substrates (p NA)
Marta Martínez Belmonte, Eduardo C. Escudero-Adán, Jordi Benet-Buchholz, Arjan W. Kleij
Published Online: Oct 14 2009 1:48PM
DOI: 10.1002/ejic.200900862

	The Zn(salphen)-templated synthesis and solution and solid-phase analysis of a series of unusual trinuclear supramolecular assemblies is reported. Under suitable conditions, a non-symmetrical Zn complex comprising two monoanionic pyridine-alcohol ligands is formed, which combines with two Zn(salphen) units to provide the Zn3 structures (see figure). The scope and mechanism of formation related to this templated process have been investigated.

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Complex Chalcogenides

Ordering Phenomena in Complex Chalcogenides - the Showcase of A₂In₁₂Q₁₉ (A = K, Tl, NH₄; Q = Se, Te) and Pseudobinary In₂Q₃ (p NA)
Lorenz Kienle, Marc Schlosser, Manolis J. Manos, Christos D. Malliakas, Viola Duppel, Christof Reiner, Hans-Jörg Deiseroth, Mercouri G. Kanatzidis, Klemens Kelm, Arndt Simon
Published Online: Oct 5 2009 11:44AM
DOI: 10.1002/ejic.200900721

	From order to disorder and back: A combined approach of electron microscopy and X-ray diffraction was applied for the characterization of highly complex chalcogenide phases. In the course of observations, a new structural variant of (NH4)2In12Se19 was produced in situ, and the mechanism of structure formation was analyzed by electron microscopy.

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Retractions

Retraction: Detailed Mössbauer Characterization of Fe²⁺Fur, the Active Form of the Ferric Uptake Regulation Protein from E. coli and Density Functional Calculations on Some Related Models (p NA)
Olivier Horner, Jean-Louis Oddou, Claudine Jeandey, Isabelle Michaud-Soret, Jean-Marie Mouesca
Published Online: Nov 6 2009 8:36AM
DOI: 10.1002/ejic.200901020

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