Zintl-type P73– complexes were synthesized from direct activation of P4 by lanthanum and lutetium naphthalene complexes. The P73– complexes showed fluxional behavior dependent on the rare-earth metal.
[Full Paper]
Wenliang Huang, Paula L. Diaconescu
Eur. J. Inorg. Chem., May 22, 2013, DOI: 10.1002/ejic.201300225. Read article.
Oxidation of (IP–)2Al(CH3) (IP = iminopyridine) with TrBPh4 (Tr = trityl) affords the C–C-coupled kinetic product [(IP)(Tr-IP)Al(CH3)][BPh4] in which the trityl radical and the IP– radical have undergone C–C bond formation. Oxidation of (IP–)2Al(CH3) with TrBArF24 affords the thermodynamic product [(IP)(IP–)Al(CH3)][BarF24] {BArF24 = tetrakis[(3,5-trifluoromethyl)phenyl]borate}.
[Short Communication]
Thomas W. Myers, Gereon M. Yee, Louise A. Berben
Eur. J. Inorg. Chem., May 22, 2013, DOI: 10.1002/ejic.201300192. Read article.
The transformation of VIII azides to the corresponding VV nitrides was investigated through isotopic labeling crossover experiments, SQUID magnetization, and multifrequency/high-field EPR studies. While Lewis bases inhibit the azide-to-nitride transformation, nitride complexes are formed by a bimetallic mechanism. Stoichiometric Lewis acid and catalytic amount of VII complex also rendered azide-to-nitride formation. However, Lewis bases inhibit formation of nitride product.
[Full Paper]
Ba L. Tran, J. Krzystek, Andrew Ozarowski, Chung-Hsing Chen, Maren Pink, Jonathan A. Karty, Joshua Telser, Karsten Meyer, Daniel J. Mindiola
Eur. J. Inorg. Chem., May 22, 2013, DOI: 10.1002/ejic.201300178. Read article.
Mo carbonyl complexes with mixed N-heterocyclic carbene (NHC)/phosphane ligands and those with pure NHC and phosphane ligands are compared. Whereas the σ-donor strengths of phosphane and carbene groups are comparable, the π-acceptor interactions of the carbene moieties are exactly canceled by π-donor interactions.
[Full Paper]
Christian Gradert, Jan Krahmer, Frank D. Sönnichsen, Christian Näther, Felix Tuczek
Eur. J. Inorg. Chem., May 22, 2013, DOI: 10.1002/ejic.201300177. Read article.
![Activating Azides and Alkynes for the Click Reaction with [Cu(aNHC)2I] or [Cu(aNHC)2]+ (aNHC = Triazole-Derived Abnormal Carbenes): Structural Characterization and Catalytic Properties](http://www.wiley-vch.de/util/hottopics/img/ejic201300150.jpg "Activating Azides and Alkynes for the Click Reaction with [Cu(aNHC)2I] or [Cu(aNHC)2]+ (aNHC = Triazole-Derived Abnormal Carbenes): Structural Characterization and Catalytic Properties")
Cationic copper(I) complexes containing two triazolylidene carbenes of the abnormal type are shown to be excellent catalysts for the [3+2] cycloaddition reaction between azides and alkynes. A range of azides and a couple of alkynes are activated by these copper(I) complexes towards the catalytic formation of the corresponding substituted 1,2,3-triazoles.
[Full Paper]
Stephan Hohloch, Damaris Scheiffele, Biprajit Sarkar
Eur. J. Inorg. Chem., May 22, 2013, DOI: 10.1002/ejic.201300150. Read article.
A highly reactive phosphanylamide-supported Zr/Co complex has been shown to react with alcohols, thiols, peroxides, and disulfides by means of a dissociative electron-transfer process occurring at Zr. A range of products are formed depending on the identity of the substrate, including both one- and two-electron oxidized products.
[Full Paper]
J. Wesley Napoline, Jeremy P. Krogman, Rena Shi, Subramaniam Kuppuswamy, Mark W. Bezpalko, Bruce M. Foxman, Christine M. Thomas
Eur. J. Inorg. Chem., May 22, 2013, DOI: 10.1002/ejic.201300122. Read article.
Dioxomolybdenum(VI) complexes with acylpyrazolonate ligands have been synthesized, characterized, and tested as catalysts in the deoxygenation of styrene oxide with triphenylphosphane as the oxygen acceptor.
[Full Paper]
Lily Hills, Raquel Moyano, Francisco Montilla, Antonio Pastor, Agustín Galindo, Eleuterio Alvarez, Fabio Marchetti, Claudio Pettinari
Eur. J. Inorg. Chem., May 21, 2013, DOI: 10.1002/ejic.201300098. Read article.
New synthetic routes to a series of bis(pentafluoroethyl)phosphanes have been developed and the structures of two of them, (C2F5)2PH and the phosphinous acid (C2F5)2POH, were studied by gas electron diffraction, making use of molecular dynamics calculations to support data analysis in an improved approach.
[Full Paper]
Alexander V. Zakharov, Yury V. Vishnevskiy, Nadine Allefeld, Julia Bader, Boris Kurscheid, Simon Steinhauer, Berthold Hoge, Beate Neumann, Hans-Georg Stammler, Raphael J. F. Berger, Norbert W. Mitzel
Eur. J. Inorg. Chem., May 21, 2013, DOI: 10.1002/ejic.201300364. Read article.
Chiral tetradentate dianionic ligands of the diamine-diphenolato and diamine-diolato families based on the (R,R)-2,2'-bipyrrolidine core led to chiral-at-metal complexes of the type [{ONNO}Zn] as single diastereomers supporting a predetermined chiral induction from the bipyrrolidine core to the helical ligand wrapping.
[Full Paper]
Ekaterina Sergeeva, Konstantin Press, Israel Goldberg, Moshe Kol
Eur. J. Inorg. Chem., May 21, 2013, DOI: 10.1002/ejic.201300151. Read article.
Two polyoxopalladates {Pd12XIII} have been synthesized by using Cr3+ and In3+ ions as structural directing agents. The coordination configuration of the central metal ions influenced by their ionic radii can affect the cluster stability, as shown by their collision-induced dissociation MS/MS spectra. This approach may help us to understand the stability and dissociation of polyoxopalladates.
[Full Paper]
Zhengguo Lin, Bo Wang, Jie Cao, Baokuan Chen, Chong Xu, Xianqiang Huang, Yanxuan Fan, Changwen Hu
Eur. J. Inorg. Chem., May 21, 2013, DOI: 10.1002/ejic.201300372. Read article.
YAH: Alkyl/hydrido exchange readily takes place when the yttrium methyl complexes (C5Me5)2YMe(thf), [(C5Me5)YMe2]3, and [YMe3]n are treated with the amidoalane HAl[N(SiMe3)2]2. The resulting heterobimetallics catalyze the addition of the amidoalane across 1-octene, as shown for (C5Me5)2Y(μ-H)2Al(Me)[N(SiMe3)2].
[Short Communication]
Christoph Schädle, Reiner Anwander
Eur. J. Inorg. Chem., May 17, 2013, DOI: 10.1002/ejic.201300504. Read article.
Thermal or photodecomposition of 2,2'-azobis(2-methylpropionitrile) (AIBN) is used as a source of cyanide anions in the synthesis of copper(I)–cyanide frameworks. The reported methodology utilizes the direct reduction of CuII(aa)(NN)X (aa = deprotonated amino acid, NN = bidentate nitrogen-based ligand, X = Cl or Br) complexes by AIBN/ascorbic acid to yield six novel coordination networks.
[Short Communication]
Aman Kaur, Tomislav Pintauer
Eur. J. Inorg. Chem., May 17, 2013, DOI: 10.1002/ejic.201300495. Read article.
{Pyrenetetrasulfonate(PyTS)/ZnS}n ultrathin films have been fabricated by a two-step procedure of layer-by-layer assembly of PyTS with Zn2Al layered double hydroxide, followed by in situ sulfurization with H2S. Gas-sensing measurements of the as-prepared (PyTS/ZnS)n films indicate that they selectively respond to ethanol gas at a relatively low temperature of 70 °C.
[Full Paper]
Ya-Ping Xiao, Li-Min Zhang, Ying Guo, Yu-Fei Song
Eur. J. Inorg. Chem., May 17, 2013, DOI: 10.1002/ejic.201300053. Read article.
![Synthesis and Characterisation of Selected Group 4 Metallocene Complexes with 1,2-Bis(4',4',5',5'-tetramethyl[1',3',2']dioxaborolan-2'-yl)acetylene](http://www.wiley-vch.de/util/hottopics/img/ejic201300236.jpg "Synthesis and Characterisation of Selected Group 4 Metallocene Complexes with 1,2-Bis(4',4',5',5'-tetramethyl[1',3',2']dioxaborolan-2'-yl)acetylene")
Group 4 metallocenes and bis(tetramethyldioxaborolanyl)acetylene gave different products: “Cp2Ti” afforded a dihydroindenyl complex. “rac-(ebthi)Ti”, “Cp*2Ti” and “Cp2Zr(py)” led to metallacyclopropenes, whereas “Cp2Zr” and “rac-(ebthi)Zr” yielded metallacyclopentadienes. One of the titanacyclopropenes reacts with CO2 to a titanacyclofuranone.
[Full Paper]
Kai Altenburger, Perdita Arndt, Anke Spannenberg, Wolfgang Baumann, Uwe Rosenthal
Eur. J. Inorg. Chem., May 16, 2013, DOI: 10.1002/ejic.201300236. Read article.
A novel synthetic route to terpyridine ligands is reported. Pyridine building blocks are interlinked by Suzuki–Miyaura cross-coupling reactions. The potential of the method is demonstrated by assembling the 4,4″-disubstituted terpyridine ligands shown, which are subsequently converted into their homoleptic FeII complexes.
[Full Paper]
Gero D. Harzmann, Markus Neuburger, Marcel Mayor
Eur. J. Inorg. Chem., May 16, 2013, DOI: 10.1002/ejic.201300231. Read article.
The N,N-trans and N,N-cis isomers of [Ir(ppy0)2(PP)]+ (ppy0 = 2-phenylpyridine ligand, PP = diphosphane ligand) have markedly different photophysical properties, which were investigated by a DFT/time-dependent DFT (TD-DFT) approach. Their different quantum phosphorescence efficiencies (ΦPL) are interpreted with their different radiative (kr) and nonradiative (knr) rates.
[Full Paper]
Xiaochun Qu, Yuqi Liu, Gahungu Godefroid, Yanling Si, Xiaohong Shang, Xue Wu, Zhijian Wu
Eur. J. Inorg. Chem., May 16, 2013, DOI: 10.1002/ejic.201300159. Read article.
The first terminal organometallic alkylphosphanylidenetantalum(V) complexes are obtained with cyclohexyl and isopropyl groups at phosphorus, whereas adamantyl and tert-butyl substituents result in the formation of a paramagnetic tantalum(IV) complex. DFT studies show that the terminal cyclohexyl and isopropyl phosphanylidene complexes are stable towards dimerization and dissociation.
[Short Communication]
Anne Grundmann, Menyhárt B. Sárosi, Peter Lönnecke, René Frank, Evamarie Hey-Hawkins
Eur. J. Inorg. Chem., May 15, 2013, DOI: 10.1002/ejic.201300500. Read article.
The particle sizes in cyano-bridged coordination polymers consisting of NiII–C≡N–FeII units are precisely controlled from 20 to 500 nm by changing the amount of sodium citrate added as a chelating agent and/or by using a different Fe source. Our synthetic concept is widely applicable to other coordination polymers, which would be beneficial to various applications in the future.
[Short Communication]
Ya-Dong Chiang, Ming Hu, Yuichiro Kamachi, Shinsuke Ishihara, Kimiko Takai, Yoshihiro Tsujimoto, Katsuhiko Ariga, Kevin C.-W. Wu, Yusuke Yamauchi
Eur. J. Inorg. Chem., May 15, 2013, DOI: 10.1002/ejic.201300112. Read article.
Iron(II) clathrochelates with two and six inherent pentafluorophenyl substituents were obtained by copper-promoted perfluoroarylation of their iodine-containing macrobicyclic precursors and characterized by analytical and spectral methods and X-ray diffraction.
[Full Paper]
Oleg A. Varzatskii, Irina N. Denisenko, Sergey V. Volkov, Alexander S. Belov, Alexander V. Dolganov, Anna V. Vologzhanina, Valentin V. Novikov, Yurii N. Bubnov, Yan Z. Voloshin
Eur. J. Inorg. Chem., May 15, 2013, DOI: 10.1002/ejic.201300189. Read article.
New halido-bridged mixed-valence CuI–CuII coordination polymers with 1D infinite chain structures have been synthesized and structurally characterized The complexes show a relatively strong antiferromagnetic interaction and interesting semiconducting behavior. These coordination polymers were applied as sensitizing materials for DSSCs.
[Full Paper]
Naoya Tanaka, Takashi Okubo, Haruho Anma, Kyung Ho Kim, Yoshie Inuzuka, Masahiko Maekawa, Takayoshi Kuroda-Sowa
Eur. J. Inorg. Chem., May 15, 2013, DOI: 10.1002/ejic.201300188. Read article.
Cyanotetrazolate (ctz) is a versatile ligand towards CuII ions and allows different kinds of linkage. Eight complexes and coordination polymers are presented with structures representing 1D chain motifs, 2D layered structures, mononuclear and dinuclear complexes. The complexes show different magnetic coupling phenomena at low temperatures.
[Full Paper]
Barbara Szafranowska, Johannes Beck
Eur. J. Inorg. Chem., May 15, 2013, DOI: 10.1002/ejic.201201483. Read article.
A series of new half-sandwich RuII complexes containing sulfonamide ligands were synthesized and characterized by NMR and FTIR spectroscopy and elemental analysis, and two of the complexes were further analyzed by X-ray diffraction. We investigated the catalytic activity of these complexes in the transfer hydrogenation of a few acetophenone derivatives with the use of 2-propanol in the presence of base.
[Full Paper]
Serkan Dayan, Nilgun Ozpozan Kalaycioglu, Jean-Claude Daran, Agnès Labande, Rinaldo Poli
Eur. J. Inorg. Chem., May 14, 2013, DOI: 10.1002/ejic.201300266. Read article.
Donor–acceptor bonds in the complexes of normal and abnormal N-heterocyclic carbenes with tricoordinate group 13 elements (B, Al and Ga) have been studied by quantum chemistry. The substituents attached to the group 13 atoms are found to have a profound effect on the strengths of the donor–acceptor bonds.
[Full Paper]
Satyajit Sarmah, Ankur Kanti Guha, Ashwini K. Phukan
Eur. J. Inorg. Chem., May 14, 2013, DOI: 10.1002/ejic.201300329. Read article.
Cobalt diglyoximate complexes connected by aluminum bridges were synthesized. The redox chemistry of these species is dependent on the number of aluminum centers and the nature of the ancillary ligand coordinated to aluminum. Proton reduction to hydrogen was observed and compared to BF2- and proton-bridged analogs.
[Full Paper]
Paul Kelley, Michael W. Day, Theodor Agapie
Eur. J. Inorg. Chem., May 14, 2013, DOI: 10.1002/ejic.201300309. Read article.
MnIII compounds of N,N'-bis(pyridoxylidene)ethylenediamine and N,N'-bis(pyridoxylidene)-1,3-propanediamine show a quasireversible MnIII/MnII couple at ca. 0 V (vs. Ag/AgCl) and two to three overlapping oxidations at 1.0–1.3 V, which are assigned to MnIII/MnIV and phenolate oxidations.
[Full Paper]
Sumita Naskar, Subhendu Naskar, Ray J. Butcher, Montserrat Corbella, Arturo Espinosa Ferao, Shyamal Kumar Chattopadhyay
Eur. J. Inorg. Chem., May 14, 2013, DOI: 10.1002/ejic.201300047. Read article.
The insertion of CO2 into iridium hydrides has been proposed as a crucial step in the iridium-catalyzed hydrogenation of CO2. We used DFT to explore the mechanism of CO2 insertion into five-coordinate iridium(III) dihydrides and four-coordinate iridium(I) monohydrides with pincer ligands, and also calculated the catalytic cycle for thermal CO2 hydrogenation starting from an iridium(III) dihydride.
[Full Paper]
Wesley H. Bernskoetter, Nilay Hazari
Eur. J. Inorg. Chem., May 13, 2013, DOI: 10.1002/ejic.201300170. Read article.
The niobium nitride complex prepared from N2 was protonated to generate NH3, while the reaction with methyl iodide gave the methyl imide complex. Exposure of the imide complex to CO2 gave the ureate complex along with the oxo-bridged dinuclear complex.
[Full Paper]
Fumio Akagi, Shoui Suzuki, Yutaka Ishida, Tsubasa Hatanaka, Tsukasa Matsuo, Hiroyuki Kawaguchi
Eur. J. Inorg. Chem., May 10, 2013, DOI: 10.1002/ejic.201300172. Read article.
In N,N'-bis(diisopropylphenyl)amidinates and guanidinates of calcium the metal center is effectively shielded. Therefore drastic reaction conditions are required, with the disadvantage that side reactions such as ether cleavage and subsequent reactions also occur.
[Full Paper]
Carsten Glock, Claas Loh, Helmar Görls, Sven Krieck, Matthias Westerhausen
Eur. J. Inorg. Chem., May 10, 2013, DOI: 10.1002/ejic.201300080. Read article.
![The Al(ORF)3/H2O/Phosphane [RF = C(CF3)3] System – Protonation of Phosphanes and Absolute Brønsted Acidity](http://www.wiley-vch.de/util/hottopics/img/ejic201300031.jpg "The Al(ORF)3/H2O/Phosphane [RF = C(CF3)3] System – Protonation of Phosphanes and Absolute Brønsted Acidity")
Small donor ligands such as Ph2MeP, Ph3P, Ph3As, or even H2O form classical donor–acceptor adducts with the Lewis superacid Al(ORF)3 [RF = C(CF3)3]. FLP-like (FLP = frustrated Lewis pair) combinations of this Lewis acid, phosphanes, and water then lead to [HPR3]+ and two new weakly coordinating anions [HOAl(ORF)3]– and [(FRO)3Al(μ-OH)Al(ORF)3]–. The absolute acidity of H2O–Al(ORF)3 is evaluated.
[Full Paper]
Anne Kraft, Josephine Possart, Harald Scherer, Jennifer Beck, Daniel Himmel, Ingo Krossing
Eur. J. Inorg. Chem., May 10, 2013, DOI: 10.1002/ejic.201300031. Read article.
CV, AC voltammetry, DC polarography and impedance spectroscopy were utilized to elucidate the mechanism, stability constants and heterogeneous rate constants of the charge transfer of the reduction/oxidation of the EuIII/EuII ion pair in the presence the newly developed ligands 1,4-DOTA(GAC12)2 and 1,7-DOTA(GAC12)2 with potential use as MRI contrast agents.
[Full Paper]
Miroslav Gál, Filip Kielar, Romana Sokolová, Šárka Ramešová, Viliam Kolivoška
Eur. J. Inorg. Chem., May 10, 2013, DOI: 10.1002/ejic.201300252. Read article.
![Lewis Bases Trigger Intramolecular CH–Bond Activation: (tBu3SiO)2W=NtBu [rlhar2] (tBu3SiO)(κO,κC-tBu2SiOCMe2CH2)HW=NtBu](http://www.wiley-vch.de/util/hottopics/img/ejic201300234.jpg "Lewis Bases Trigger Intramolecular CH–Bond Activation: (tBu3SiO)2W=NtBu [rlhar2] (tBu3SiO)(κO,κC-tBu2SiOCMe2CH2)HW=NtBu")
The symmetry-forbidden cyclometalation of (silox)2W=NtBu (1, silox = OSitBu3) to (silox)(tBuN)W(H)(κO,κC-OSitBu2CMe2CH2) (2) and the oxidative addition of dihydrogen to give (silox)2(tBuN=)WH2 (3) are catalyzed by phosphane bases with cone angles < 160°. Quantum mechanics/molecular mechanics (QM/MM) calculations support the experimental findings and show that Lewis bases promote σ/π mixing.
[Full Paper]
Michael P. Marshak, Devon C. Rosenfeld, Wesley D. Morris, Peter T. Wolczanski, Emil B. Lobkovsky, Thomas R. Cundari
Eur. J. Inorg. Chem., May 10, 2013, DOI: 10.1002/ejic.201300234. Read article.
The synthesis of MnIII complexes capped by tetradentate ligands and assembled by phosphinate ligands is reported. The phosphinate coordination mode is influenced by the steric hindrance of both the phosphinate and the tetradentate ligands. Two 1D polymeric structures have been obtained, one of which presents single chain magnet (SCM) behaviour.
[Full Paper]
Sébastien Richeter, Joulia Larionova, Jérôme Long, Arie van der Lee, Dominique Leclercq
Eur. J. Inorg. Chem., May 10, 2013, DOI: 10.1002/ejic.201300246. Read article.
Pyridine-substituted dithiolene gold complex [Au(4-pdddt)2] shows three redox processes corresponding to the interconversion between dianionic, monoanionic, neutral and cationic states, the last one corresponding to a polymerised species obtained as an electrodeposited film.
[Short Communication]
Sandrina Oliveira, Mónica L. Afonso, Sandra I. G. Dias, Isabel C. Santos, Rui T. Henriques, Sandra Rabaça, Manuel Almeida
Eur. J. Inorg. Chem., May 10, 2013, DOI: 10.1002/ejic.201300222. Read article.
KPbBP2O8 is synthesized and its structure is determined by single-crystal X-ray diffraction. Thermal and XRD analysis show that KPbBP2O8 melts congruently. IR and UV/Vis spectroscopy and second-harmonic generation measurements are also performed on the reported material.
[Full Paper]
Hongyi Li, Yi Zhao, Shilie Pan, Hongping Wu, Hongwei Yu, Fangfang Zhang, Zhihua Yang, Kenneth R. Poeppelmeier
Eur. J. Inorg. Chem., May 10, 2013, DOI: 10.1002/ejic.201300009. Read article.
Diaza-18-crown-6 ligands functionalised with diaminomethane linkers are unstable in the presence of selected divalent transition-metal ions. Pretreatment of the ligands with potassium salts prevents degradation by blocking the central coordination region. Iodide redox chemistry also affects the coordination-polymer motif.
[Full Paper]
William J. Gee, Stuart R. Batten
Eur. J. Inorg. Chem., May 10, 2013, DOI: 10.1002/ejic.201201564. Read article.
The coordination properties of phosphanylborane ligands in newly synthesized tungsten carbonyl nitrosyl complexes are explored by multinuclear NMR and IR spectroscopy, single-crystal X-ray structure analyses, and DFT calculations.
[Full Paper]
Rajkumar Jana, Olivier Blacque, Yanfeng Jiang, Heinz Berke
Eur. J. Inorg. Chem., May 10, 2013, DOI: 10.1002/ejic.201201565. Read article.
The hydrolytic properties of half-sandwich [M(η6-arene)(H2O)3]2+ (M = Ru, Os; η6-arene = benzene, toluene, 1-methyl-4-isopropylbenzene, 1,3,5-triisopropylbenzene) or [Ir(η5-Cp*)(H2O)3]2+ (Cp* = pentamethylcyclopentadienyl) cations can be tuned by the proper selection of the arene system and by modification of the metal ion to make them more resistant to hydrolysis.
[Full Paper]
Linda Bíró, Attila J. Godó, Zsolt Bihari, Eugenio Garribba, Péter Buglyó
Eur. J. Inorg. Chem., May 10, 2013, DOI: 10.1002/ejic.201201527. Read article.
[Short Communication]
Richard J. Burford, Warren E. Piers, Masood Parvez
Eur. J. Inorg. Chem., May 10, 2013, DOI: 10.1002/ejic.201300152. Read article.
[Full Paper]
Lena J. Daumann, James A. Larrabee, Peter Comba, Gerhard Schenk, Lawrence R. Gahan
Eur. J. Inorg. Chem., May 08, 2013, DOI: 10.1002/ejic.201300280. Read article.
![The First Example of the Two-Electron Reduction of a Phosphaalkyne – Synthesis and Structural Characterisation of the Diuranium(IV) Pentalene Complex [(U{η5-C5Me5}{η8-C8H4(SiiPr3-1,4)2})2(μ-η2:η1-tBuCP)]](http://www.wiley-vch.de/util/hottopics/img/ejic201300256.jpg "The First Example of the Two-Electron Reduction of a Phosphaalkyne – Synthesis and Structural Characterisation of the Diuranium(IV) Pentalene Complex [(U{η5-C5Me5}{η8-C8H4(SiiPr3-1,4)2})2(μ-η2:η1-tBuCP)]")
The two-electron reduction of the phosphaalkyne tBuC≡P by the UIII mixed-sandwich complex [U(η5-C5Me5){η8-C8H4(SiiPr3)2}] yields the diuranium(IV) product [(U{η5-C5Me5}{η8-C8H4(SiiPr3)2})2(μ-tBuCP)], which contains a μ-η2:η1-ligated phosphaalkene dianion.
[Full Paper]
Nikolaos Tsoureas, Alexander F. R. Kilpatrick, Owen T. Summerscales, John F. Nixon, F. Geoffrey N. Cloke, Peter B Hitchcock
Eur. J. Inorg. Chem., May 08, 2013, DOI: 10.1002/ejic.201300256. Read article.
[Full Paper]
David T. Walker, Rohan S. Dassanayake, Kamille A. Garcia, Riya Mukherjee, Nicola E. Brasch
Eur. J. Inorg. Chem., May 08, 2013, DOI: 10.1002/ejic.201300254. Read article.
[Full Paper]
Ioana Barbul, Richard A. Varga, Cristian Silvestru
Eur. J. Inorg. Chem., May 08, 2013, DOI: 10.1002/ejic.201300245. Read article.
[Full Paper]
Markus Plois, Robert Wolf, Waldemar Hujo, Stefan Grimme
Eur. J. Inorg. Chem., May 08, 2013, DOI: 10.1002/ejic.201300233. Read article.
The new luminescent material La3Cl(CN2)O3:Ln 5 mol-% (Ln = Eu3+ or Tb3+) was successfully synthesized by a simple reaction of LaOCl with Li2CN2 (+ LnCl3).
[Full Paper]
Mariusz Kubus, David Enseling, Thomas Jüstel, H.-Jürgen Meyer
Eur. J. Inorg. Chem., May 08, 2013, DOI: 10.1002/ejic.201300224. Read article.
[Full Paper]
Marco Bortoluzzi, Franco Ghini, Mohammad Hayatifar, Fabio Marchetti, Guido Pampaloni, Stefano Zacchini
Eur. J. Inorg. Chem., May 08, 2013, DOI: 10.1002/ejic.201300219. Read article.
[Short Communication]
Koji Yamamoto, Yu Shibata, Yuki Kashiwa, Ai Kondo, Hayato Tsurugi, Kazushi Mashima
Eur. J. Inorg. Chem., May 08, 2013, DOI: 10.1002/ejic.201300210. Read article.
[Microreview]
Thomas L. Gianetti, Henry S. La Pierre, John Arnold
Eur. J. Inorg. Chem., May 08, 2013, DOI: 10.1002/ejic.201300202. Read article.
[Short Communication]
Amanda R. Corcos, Amanda Kae Musch Long, Ilia A. Guzei, John F. Berry
Eur. J. Inorg. Chem., May 08, 2013, DOI: 10.1002/ejic.201300180. Read article.
[Full Paper]
Emmanuel Terazzi, Amir Zaïm, Bernard Bocquet, Johan Varin, Laure Guénée, Thibault Dutronc, Jean-François Lemonnier, Sébastien Floquet, Emmanuel Cadot, Benoît Heinrich, Bertrand Donnio, Claude Piguet
Eur. J. Inorg. Chem., May 08, 2013, DOI: 10.1002/ejic.201300176. Read article.
[Microreview]
Sébastien Ladouceur, Eli Zysman-Colman
Eur. J. Inorg. Chem., May 08, 2013, DOI: 10.1002/ejic.201300171. Read article.
[Full Paper]
Daniel Martin, Julian Kleemann, Elise Abinet, Thomas P. Spaniol, Laurent Maron, Jun Okuda
Eur. J. Inorg. Chem., May 08, 2013, DOI: 10.1002/ejic.201300167. Read article.
[Short Communication]
Ashley M. Wright, Joshua S. Page, Jeremiah J. Scepaniak, Guang Wu, Trevor W. Hayton
Eur. J. Inorg. Chem., May 08, 2013, DOI: 10.1002/ejic.201300163. Read article.
[Full Paper]
Rupam Sen, Debraj Saha, Dasarath Mal, Paula Brandão, Guillaume Rogez, Zhi Lin
Eur. J. Inorg. Chem., May 08, 2013, DOI: 10.1002/ejic.201300123. Read article.
[Full Paper]
Madhappan Santha Moorthy, Mi-Ju Kim, Jae-Ho Bae, Sung Soo Park, Nagappan Saravanan, Sun-Hee Kim, Chang-Sik Ha
Eur. J. Inorg. Chem., May 08, 2013, DOI: 10.1002/ejic.201300118. Read article.
[Microreview]
Benedict M. Gardner, Stephen T. Liddle
Eur. J. Inorg. Chem., May 08, 2013, DOI: 10.1002/ejic.201300111. Read article.
[Full Paper]
Yuan-Yuan Zhu, Chang Cui, Ning Li, Bing-Wu Wang, Zhe-Ming Wang, Song Gao
Eur. J. Inorg. Chem., May 08, 2013, DOI: 10.1002/ejic.201300107. Read article.
![Electronic Elements Governing the Binding of Small Molecules to a [Fe]-Hydrogenase Mimic](http://www.wiley-vch.de/util/hottopics/img/ejic201300081.jpg "Electronic Elements Governing the Binding of Small Molecules to a [Fe]-Hydrogenase Mimic")
[Full Paper]
Matthew D. Wodrich, Xile Hu
Eur. J. Inorg. Chem., May 08, 2013, DOI: 10.1002/ejic.201300081. Read article.
[Full Paper]
Claudia Köthe, Ramona Metzinger, Christian Limberg
Eur. J. Inorg. Chem., May 08, 2013, DOI: 10.1002/ejic.201300064. Read article.
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Zsuzsa Majer, Gábor Szilvágyi, László Benedek, Antal Csámpai, Miklós Hollósi, Elemér Vass
Eur. J. Inorg. Chem., May 08, 2013, DOI: 10.1002/ejic.201300057. Read article.
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Scott P. Semproni, Paul J. Chirik
Eur. J. Inorg. Chem., May 08, 2013, DOI: 10.1002/ejic.201300046. Read article.
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Tsubasa Hatanaka, Yasuhiro Ohki, Kazuyuki Tatsumi
Eur. J. Inorg. Chem., May 08, 2013, DOI: 10.1002/ejic.201300045. Read article.
We measured the nucleophilic properties of the terminal amine of a Ni(peptide) complex as a tool to elucidate the ligation sites of the cation.
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Zeev Gaisin, Gary Gellerman, Dan Meyerstein
Eur. J. Inorg. Chem., May 08, 2013, DOI: 10.1002/ejic.201300039. Read article.
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Di Li, Xiaojuan Bai, Chengsi Pan, Yongfa Zhu
Eur. J. Inorg. Chem., May 08, 2013, DOI: 10.1002/ejic.201300020. Read article.
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Yanjun Hou, Jing Shi, Wenyi Chu, Zhizhong Sun
Eur. J. Inorg. Chem., May 08, 2013, DOI: 10.1002/ejic.201300013. Read article.
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Jan Dietrich, Anica Wünsche von Leupoldt, Markus Grabolle, Ute Resch-Genger, Katja Heinze
Eur. J. Inorg. Chem., May 08, 2013, DOI: 10.1002/ejic.201201531. Read article.
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Wesley A. Hoffert, Michael T. Mock, Aaron M. Appel, Jenny Y. Yang
Eur. J. Inorg. Chem., May 08, 2013, DOI: 10.1002/ejic.201201499. Read article.
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Alyssia M. Lilio, Kyle A. Grice, Clifford P. Kubiak
Eur. J. Inorg. Chem., May 08, 2013, DOI: 10.1002/ejic.201201208. Read article.
3,4-Dicyano-1,2,5-telluradiazole and its adducts with pyridine, chloride, and bromide ions have been isolated, and the supramolecular structures investigated by X-ray crystallography.
A series of novel, low-valent germanium compounds have been obtained by the reaction of Ge[N(SiMe3)2]2 with various diamines or by the metathesis reaction of [GeCl2⋅dioxane] with lithium amides. The oxidative insertion, [1+4] cycloaddition, and oxidation reactions of the synthesized germylenes were investigated. All the synthesized germylenes are monomeric.
Definitely different: As the chemistry of trifluoromethyl–TM derivatives continues to develop, it becomes clearer that methyl and trifluoromethyl ligands (CH3 vs. CF3) exhibit more differences than similarities in their chemical behavior.
The Zn(salphen)-mediated synthesis of 3-substituted indoles by using a multicomponent reaction approach is reported. The reaction parameters were investigated and the selectivity for the 3-CR product was examined under various conditions. Selectivity for the target compound is significantly compromised by side-product formation due to in situ reaction of the intermediate species with malononitrile, which affords N-heterocyclic structures.
Isostructural compounds Fe7Sb3(PO4)3O6Cl3 and Fe7Sb3(PO4)3O6Br3 are the first iron phosphates containing SbIII. Tubular Fe7(PO4)3O6X3 units (X = Cl, Br) are linked by SbO4 groups to build up a 3D framework. The Fe atoms are arranged to resemble an armchair-type (3,3) nanotube.
A large diversity of transition-metal complexes bearing the dinucleating tetra-N-dentate ligand 3,5-bis(2-pyridyl)pyrazole (Hbpp) is described. Their applications in the field of catalysis as hydrogen-transfer, epoxidation, and water-oxidation catalysts are highlighted. Further, their applications in fundamental coordination chemistry are also discussed.
The selective preparation of (μ-η2:η2-peroxido)dicopper(II) and bis(μ-oxido)dicopper(III) species is regulated by the substituent groups of triaminocyclohexane derivative ligands. Their structural and spectroscopic features and reactivity are discussed.
PdII and PtII complexes containing a trans-chelating bis(pyridyl) ligand bpib have been synthesised. The catalytic reactivity of bpib in PdII for arene acetoxylation has been examined and compared with that of 2,2'-bipy.
Cyclometalated RuII coordination compounds of the general formula [Ru(bpy)2(C∧N)]PF6 {C∧N = 2-phenylpyridine (1), 2-(2,4-difluorophenyl)pyridine (2), 2-(4-methoxyphenyl)-5-methylpyridine (3), benzo[h]quinoline (4); bpy = 2,2'-bipyridine} have been synthesized, structurally and electrochemically characterized, and examined with spectroscopic techniques including ultrafast transient absorption.
An overview is given on the synthesis of key precursors for use as ligands or building blocks in ferrocene chemistry. The review is a personal account detailing the reasons for synthetic routes that have been developed over 30 years. The focus is on the preparation of ferrocenylphosphanes; however, also included is a section on the preparation of compounds as precursors for material science.
The outstanding affinity of receptor 1H66+ towards ReO4–, in an acidic water solution, opens new perspectives for the development of selective materials for the extraction and recovery of the perrhenate anion for clinical and environmental purposes. The formation of an inclusion complex, [1H6(ReO4)](CF3SO3)5, is confirmed by X-ray diffraction studies.
The coordination chemistry of neutral phosphane adducts of phosphinidenes (phosphanylidene-σ4-phosphoranes, also known as phospha-Wittig reagents, RP=PR3) is reviewed.
The biological activity of four cisplatin-like Pt–phosphane complexes has been tested. Some of the complexes can undergo intramolecular rearrangement by virtue of the functionalized phosphanes (fully opened/fully closed forms). The results show that only the opened forms exhibit moderate activity, which is substantially retained in the cisplatin-resistant cell lines.
Towards understanding the key attributes that define the influence of N-heterocyclic carbenes on catalysis, our efforts, involving combined experimental and computational approaches, in looking into a variety of catalytic and biomedical applications of these compounds are summarized.
The dicopper complexes of two dinucleating ligands undergo a strong antiferromagnetic coupling upon formation of an imidazolato bridge. UV/Vis and EPR spectroscopy as well as electrochemical studies confirmed the potentiometric solution speciation.
Iridium–carbon sigma bond formation in supercages of faujasite-type zeolites is achieved by using a microwave-assisted ship-in-a-bottle synthesis. The successive reaction of IrIII cations in the zeolite with two ligands leads to two types of complexes in the different supercages, and the emission from these IrIII complexes can be tuned in a range from blue to green.
We provide a comprehensive overview of the synthesis and structural alignment of bulky porphyrin molecules in the interlayer space of layered hydroxide–porphyrin hybrids. Emphasis is placed on the spectral and photophysical properties of intercalated porphyrins and phthalocyanines for photobactericidal purposes, catalysis, and sensing.
![EurBest in EurJIC: Rhenium(I) and Technetium(I) Tricarbonyl Complexes with [NSO]-Type Chelators: Synthesis, Structural Characterization, and Radiochemistry](http://www.wiley-vch.de/img/news/ejic-201200056.jpg)
fac-[Re(NSO)(CO)3] complexes were synthesized with varying chelate ring size and geometry. The order of complex formation preference is: linear (6,5-membered rings) > tripodal (6,5,7-membered rings) > linear (two six-membered rings). The analogous fac-[99mTc(NSO)(CO)3] complexes were prepared in high yield and were stable in solution.
CO-releasing molecules are interesting therapeutic agents that can deliver and release CO upon stimulation. Light triggers the release of CO in different complexes [LMn(CO)3]+, where L is an N,N,N ligand. Although different amounts of CO released per complex are observed by myoglobin assay, IR spectroscopic investigation of their solutions indicates loss of all CO ligands.
A new bombesin copper complex based on a bifunctional cyclam derivative was synthesized, characterized, and evaluated for its binding affinity to bombesin receptors through in vitro cell assays with PC-3 cells.
Heterogeneous bifunctional catalysts containing metal and acid sites have great potential for the development of greener production processes, particularly for the preparation of fine chemicals. This review highlights the recent advancements and the most representative examples in the field.
![EurBest in EurJIC: Titration of Zr3(μ-OH) Hydroxy Groups at the Cornerstones of Bulk MOF UiO-67, [Zr6O4(OH)4(biphenyldicarboxylate)6], and Their Reaction with [AuMe(PMe3)]](http://www.wiley-vch.de/img/news/ejic-201200033.jpg)
Thermally stable MOF UiO-67, [Zr6O4(OH)4(bpdc)6], is well-behaved chemically in the bulk: Cornerstone (μ3-OH) hydroxy groups react quantitatively with MeMgBr with stoichiometric release of methane. Post-synthetic modification with [AuMe(PMe3)] results in partial covalent grafting of the AuI center onto the cornerstone hydroxy groups.
This review describes Eu2+-containing complexes reported in the 21st century with focus on the synthesis, reactivity, and application of these complexes.
Empty and filled hybrid cage compounds with siloxane as well as ether units between four phosphorus bridge-head atoms were obtained from the deprotonation of the cyclic siloxadiphosphane [O(SiiPr2)2PH]2 and subsequent reaction with diiodo ethers. These compounds show very different coordination behaviour depending on the length of the ether chain and the metal cation used.
A new sugar-derived ligand, with its coordination site embedded in a pyranoside cycle in the chair conformation, has been designed. Its transition-metal complexes were characterized by experimental and complexation methods and revealed a dramatic impact of the preorganization and complementarity of the carbohydrate scaffold on the metal binding.
The synthesis of a new asymmetric dinucleating ligand FloH, designed with two sets of metal ion binding groups suited to selective complexation, is reported. The site-directed generation of a heterodinuclear FeIIICuII complex is performed in highyield and purity by using FloH.
The use of microwave heating for the direct synthesis of (NHC)MCl complexes (NHC = N-heterocyclic carbene; M = Cu, Ag, Au) in very short reaction times is presented. Comparable or better yields than those reported by using conventional heating can be obtained with this protocol.
A series of cobalt(II) dimeric tetrahedral (30e) complexes were obtained in good yields and were transformed into the monomeric forms with pyridine. These complexes were characterized by SQUID, XPS, UV/Vis spectroscopy, elemental analysis, and X-ray crystallography, and were found to have high catalytic activity for Kumada–Tamao–Corriu cross-coupling reactions of aryl halides.
The reaction of AgSbF6 with the gold chloride complex of the extremely bulky N-heterocyclic carbene ligand IPr** (simplified in the figure) revealed a silver cation coordinated to a single AuCl fragment – an intermediate proposed for most gold-catalyzed organic transformations.
The reaction illustrated gives the decanuclear complexes [Cu10(bzox)10(DMF)4] and [Cu10(bzox)10] (bzoxH2 = α-benzoin oxime, DMF = N,N-dimethylformamide), which have a single-strand wheel topology, and the 1D chain [Cu(N3)(O2CPh)(MeOH)]n. The Cu10 clusters are both antiferromagnetically coupled with S = 0 ground states, whereas the 1D chain consists of ferromagnetically coupled S = 1/2 CuII ions.
Copper(I/II) complexes of varying nuclearity have been obtained with a series of tetrapodal pentadentate N-donor ligands.
Porous, organically modified silica-based mixed oxides were prepared by sol-gel processing of organotrialkoxysilanes with bridging amono groups and metal chlorides. Materials with ordered porosity and uniform mesopores were obtained with metal proportions up to about 20 %.
RhII carboxylates [Rh2{O2CCH2(OCH2CH2)2OCH3}4]n and [Rh2{O2CCH2(OCH2CH2)2OCH3}4(PPh3)] featuring ethylene glycol chains were prepared and used to generate rhodium nanoparticles using the alcohol-reducing process. Nanoparticle sizes between (3.0±0.4) and (3.9±0.4) nm were obtained.
[Fe(salten)(3-azpy)]BPh4 (1) and [Fe(salten)(4-azpy)]BPh4 (2) have been synthesized and characterized [salten = 4-azaheptamethylene-1,7-bis(salicylideneiminate), azpy = phenylazopyridine]. Both exhibit a low to high spin transition in the solid state and are predominantly high spin in solution. cis–trans isomerization of coordinated azpy leaves their spin equilibria almost unaffected.
The use of metallodendrimers is fast becoming an attractive strategy in the design of a new class of metal-based biomolecules. This review surveys illustrative examples of these multivalent biologically active molecules as metal-based drugs and as agents for biosensing, photothermal and photodynamic therapy.
The synthesis of a tBu2Sn-bridged ansa-cycloheptatrienyl-cyclopentadienyl titanium sandwich complex is presented. As a result of its tilted structure, this strained stanna[1]troticenophane is easily converted into poly(troticenylstannanes) by ring-opening polymerization and undergoes regioselective insertion of platinum(0) into the ipso-C7H6–Sn bond upon reaction with [Pt(PEt3)3].
The synthesis and characterization of Fe3O4@Tb-DOTAm-(acetylene)3 and Fe3O4@Tb-DOTAm-(Phen)3, two magnetoluminescent agents for dual imaging by MRI and confocal imaging are presented. The nanoparticles are characterized by high transverse and longitudinal relaxivities and long luminescence lifetimes ideal for time-gated spectroscopy.
Bulky monodentate phosphoramidites give very fast palladium catalysts for the Mizoroki–Heck arylation with migratory insertion as rate-limiting step.
The self-association in a tetrahedral [Cu(N-{4-nitrophenyl}pyridine-2-yl-methanimine)(PPh3)Br] complex is reported. Experimental evidence for the dimerization in solution of this complex was obtained by NMR techniques. The dimer linked by noncovalent interactions has a close similarity to that in the crystalline packing. The thermodynamic parameters obtained by VT-1H NMR suggest that this process is enthalpy driven.
Oxidative addition of 4-iodoimidazolium salts to low-valent palladium(0) provides access to abnormal NHC–palladium complexes without requiring protection of the C2 position. Hence, this site is available for further functionalisation which allows, for example, dimetallic complexes to be prepared.
The complex cis-[Ru(κ2-OAc)2(PPh3)2] acts as a precursor for the formation of the complexes trans-[Ru(κ1-OAc)(κ2-OAc)L(PPh3)2] where L is a two-electron donor, σ-donor/π-acceptor ligand. The structural and spectroscopic data of these species provide insight into the relative electron demand of the ligands L.
Cp–NHC piano-stool iron complexes were found to be efficient catalysts for the hydrosilylation of aldehydes and ketones under solvent-free conditions and by activation by light irradiation. An acceleration of the rate of the reaction was observed under neat conditions relative to those for the reactions in toluene or THF.
Dimethyl acetylenedicarboxylate reacts with 2 mol-equiv. B(C6F5)3 by C6F5 transfer to the central acetylenic C≡C bond with formation of a tail-to-tail coupled bis(boron ester enolate) system. The central hexasubstituted butadiene unit of this unique system reacts with dimethyl maleate in a Diels–Alder reaction to give a hydroquinone derivative.
Recent applications of infrared and Raman spectroscopy, as well as nuclear inelastic scattering (NIS), with respect to the study of spin-crossover (SCO) phenomena are reviewed. A special focus lies on micro- and nanostructures of SCO complexes as well as on time-dependent phenomena.