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Robert Wolf Dr. J. Chris Slootweg Dr. Andreas W. Ehlers Dr. František Hartl Dr. Bas de Bruin Dr. Martin Lutz Dr. Anthony L. Spek Prof. Dr. Koop Lammertsma Prof. Dr. 《Angewandte Chemie (International ed. in English)》2009,48(17):3104-3107
P makes it possible : The convenient oxidative synthesis of the 16‐electron organophosphorus iron sandwich complex [Fe(η4‐P2C2tBu2)2] (see structure) suggests that the elusive all‐carbon complex [Fe(η4‐C4H4)2] is a viable synthetic target.
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Nathalie M. Rocher Dr. Ekaterina I. Izgorodina Dr. Thomas Rüther Dr. Maria Forsyth Prof. Douglas R. MacFarlane Prof. Theo Rodopoulos Dr. Michael D. Horne Alan M. Bond Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(14):3435-3447
Aluminium speciation : Aluminium speciation in NTf2 ionic liquids has a strong influence on its electrodeposition from the liquid mixture. This work probed the nature of these species and proposes that the electroactive species involved are either [AlCl3(NTf2)]? or [AlCl2(NTf2)2]? (e.g., see figure).
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Qiufeng Huang Dr. Ruimao Hua Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(15):3817-3822
Economical atoms : 2‐Cyclopenten‐1‐ones, 5‐alkylidenefuran‐2(5 H)‐ones and indan‐1‐ones have been synthesized by atom‐economic reductive cyclocarbonylation of internal alkynes with carbon monoxide catalyzed by [{RhCl(CO)2}2]/CO(NH2)2 in the presence of water (see scheme).
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Dieter Himsl Dirk Wallacher Dr. Martin Hartmann Prof. Dr. 《Angewandte Chemie (International ed. in English)》2009,48(25):4639-4642
Lithium makes the difference : A simple strategy for the synthesis of lithium‐doped porous metal–organic frameworks (MOFs) is developed (see structure; C black, O red, AlO6 blue octahedra), thus paving the way for the facile preparation of lithium‐doped MOFs. Moreover, the significant increase in hydrogen adsorption predicted by theoretical calculations is observed.
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Xiaogen Huang Dr. Teresa de Haro Cristina Nevado Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(24):5904-5908
Change the ligand, change the stereochemistry : 2,3‐Bis(acetoxy)‐1,3‐dienes are obtained in a stereocontrolled manner by a novel tandem 1,2‐/1,2‐bis(acetoxy) rearrangement (see scheme, R1 and R2 are δ+ stabilizing). Upon stabilization of the reaction intermediates, the ligand attached to gold controls the stereochemistry of the alkene in the second acetate migration, that is, N‐heterocyclic carbenes (NHC) favor cis alkenes, whereas phosphine ligands selectively afford trans olefins.
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Jason L. Dutton Heikki M. Tuononen Adjunct Prof. Dr. Paul J. Ragogna Prof. 《Angewandte Chemie (International ed. in English)》2009,48(24):4409-4413
Te for two : Supported by pyridine‐ or carbene‐based ligands, tellurium‐centered dications are prepared in high yield and include a dicationic tellurium analogue of the recently synthesized “carbodicarbene”. The key to accessing these compounds is the isolation of a base‐stabilized form of TeOTf2 (see structure), a new highly electrophilic reagent for tellurium chemistry.
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Gregory M. Sandala Dr. Borislav Kovačević Dr. Danijela Barić Dr. David M. Smith Dr. Leo Radom Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(19):4865-4873
Intriguing inactivation : Calculations suggest that the ability of relatively high‐energy radical intermediates to inactivate glycerol dehydratase (GDH) may reflect a general and hitherto unidentified inactivation mechanism in the reaction of coenzyme B12‐dependent enzymes and 3‐unsaturated 1,2‐diols (see scheme; AdoCbl: adenosylcobalamin or coenzyme B12).
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Lei Gong Dr. Zhening Chen Yumei Lin Xumin He Prof. Dr. Ting Bin Wen Prof. Dr. Xin Xu Prof. Dr. Haiping Xia Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(25):6258-6266
Osmabenzenes can be easily synthesized from two η2‐coordinated olefin osmacycles in the presence of benzonitrile by means of facile hydrogen‐transfer conversions (see graphic). Mechanisms for the formation of osmabenzenes are proposed based on DFT calculations.
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Dani Peri Sigalit Meker Michal Shavit Edit Y. Tshuva Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(10):2403-2415
Carefully design your ligand! A new family of highly cytotoxic TiIV complexes demonstrates strong dependence of activity on the particular ligand employed, in which small structural modifications dramatically affect both hydrolytic behavior and biological activity (see picture). Different structure‐dependence patterns are observed for hydrolysis and cytotoxicity, which are, nonetheless, strongly related.
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Raheleh Partovi‐Nia Bin Su Dr. Fei Li Dr. Claude P. Gros Dr. Jean‐Michel Barbe Dr. Zdenek Samec Prof. Hubert H. Girault Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(10):2335-2340
Oxygen reduction : A polarized water|1,2‐dichloroethane (DCE) interface acts as a proton pump for the [Co(tpp)] (TPP=5,10,15,20‐tetraphenylporphyrinato) catalyzed O2 reduction by ferrocene (Fc) compounds to produce H2O2 (see figure; IT=ion transfer, ET=electron transfer). This system favours the collection of H2O2 by extraction immediately after its formation in DCE to the adjacent water phase.
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Giorgio Volpi Claudio Garino Dr. Luca Salassa Dr. Jan Fiedler Kenneth I. Hardcastle Prof. Roberto Gobetto Prof. Carlo Nervi Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(26):6415-6427
Luminescent ligands in IrIII cyclometalated complexes. The photophysical and photochemical properties of Ir‐cyclometalated complexes containing luminescent ligands are evaluated (see figure). Significant admixture between Ir and ligand orbitals induces an efficient intersystem crossing. Photochemical reactions performed in the presence of oxygen lead to new Ir‐cyclometalated complexes containing N(amido) groups directly bound to Ir.
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Daniel Heinrich Dr. Ulf Diederichsen Prof. Dr. Markus Georg Rudolph Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(27):6619-6625
Molecular versatility : Unusual reactivities such as hydrolysis, nucleophilic aromatic substitution, and addition reactions of human orotidine‐5′‐monophosphate decarboxylase are explained by crystal structures and involve a nucleophilic lysine residue that normally is expected to act solely as a general base (RP=phosphoribosyl, R=CO2H, CN, acetyl, N3, I; R′=OH, SH, acetyl, hydroxymethyl).