bluuebunny/crossref_metadata_2025_split huggingface dataset:
Synthesis, Characterization and Electrochemical Properties of Optically Active [60]Fullerene Organotransition Metal Complexesmer‐[(η2‐C60)M(CO)3{(−)‐DIOP}] (M = Mo, W),mer‐[(η2‐C60)M(CO)3{(+)‐DIOP}] (M = Mo, W) and [(η2‐C60)M{(−)‐DIOP}] (M = Pd, Pt) − Crystal Structure of [(η2‐C60)Pt{(−)‐DIOP}]
Authors: Song Li‐Cheng , Liu Peng‐Chong , Liu Jin‐Ting , Su Fu‐Hai , Wang Guang‐Feng , Hu Qing‐Mei , Zanello Piero , Laschi Franco , Fontani Marco 
Published: August 2003

AbstractThis paper reports on several new optically active organometallic [60]fullerene complexes that contain a chiral (+)‐DIOP or (−)‐DIOP ligand [DIOP = 2,3‐O,O′‐isopropylidene‐2,3‐dihydroxy‐1,4‐bis(diphenylphosphanyl)butane]. The Mo/W complexesmer‐[(η2‐C60)M(CO)3{(−)‐DIOP}] (1, M = Mo;2, M = W) andmer‐[(η2‐C60)M(CO)3{(+)‐DIOP}] (3, M = Mo;4, M = W) were synthesized by a photochemical reaction of a mixture of [M(CO)6], (−)‐DIOP or (+)‐DIOP and C60in chlorobenzene in 42−51% yields, whereas the Pd/Pt complexes [(η2‐C60)M{(−)‐DIOP}] (5, M = Pd;6, M = Pt) were prepared by a thermal reaction of C60with [M(PPh3)4], followed by in situ treatment of the intermediate [(η2‐C60)M(PPh3)2] with (−)‐DIOP, in toluene in > 90% yields. All the new complexes1−6were fully characterized by elemental analysis,1H (31P,13C) NMR, IR, UV/Vis and circular dichroism (CD) spectroscopy. The structure of [(η2‐C60)Pt{(−)‐DIOP}] (6) was further confirmed by X‐ray diffraction techniques. The electrochemical properties of complexes1,2,5and6were studied in dichloromethane solution. Complexes1and2display the reversible, four‐membered, one‐electron reduction sequence typical of fullerene ligands, as well as the reversible (in the cyclic voltammetric time scale) one‐electron oxidation of the outer metal fragment. Complexes5and6are less stable to the same electron transfer processes. EPR measurements suggest that in the different electrogenerated monoanions, the added electrons enter the LUMO orbitals partially contributed by the metal fragment. In addition, they confirm that the instability of the reduction intermediates is due to the release of free C60. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Syntheses, Structures and Theoretical Investigations of 1λ4,3λ4,5λ4‐Trithia‐2,4,6,8,9‐pentaazabicyclo[3.3.1]nona‐1(9),2,3,5,7‐pentaenes
Authors: Knapp Carsten , Lork Enno , Borrmann Tobias , Stohrer Wolf‐Dieter , Mews Rüdiger 
Published: August 2003

AbstractThe syntheses of the title compounds RCN5S3 with electron‐withdrawing aryl substituents [R = 2‐FC6H4 (1m), 4‐FC6H4 (1n), 2,6‐F2C6H3 (1o), C6F5 (1p), 4‐NCC6H4 (1q) and Cl3C (1r)] are described. The X‐ray structures of 1n, 1o, 1q and 1r, together with those of Me2NCN5S3 (1b) and 4‐CH3C6H4CN5S3 (1f), are reported. The experimentally determined dependence of the bond lengths on the substituents R within the bicyclic system RCN5S3 is well‐reflected in the results of the theoretical calculations (RHF, MP2, B3LYP). The bonding model developed shows that acceptor substituents do not influence bonding within the bicycle. In the solid state, two fundamentally different primary interactions of the RCN5S3 molecules are observed; “stacking” and “dimerisation”, which can be rationalised by electrostatic interactions between the CN5S3 units. However, secondary effects − the interactions between the R substituents − may be even more dominant. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Palladium(II) Complexes Containing a Pyridinyliminophosphorane Ligand
Authors: Wu Hung‐Ren , Liu Yi‐Hung , Peng Shie‐Ming , Liu Shiuh‐Tzung 
Published: August 2003

AbstractA series of new pyridinyliminophosphorane bidentate ligands with different steric environments [(2‐C6H4N)PPh2=NAr (NPN)] and their methylpalladium complexes [PdClMe(NPN)] were prepared. From the crystal structure analysis it is evident that the alkyl ligands are always trans to the pyridinyl nitrogen donor, revealing a σ‐donating ability of the iminophosphorane. However, the two Pd−Cl bonds in [PdCl2(NPN)] are essentially the same length. Cationic palladium complexes catalyzed the copolymerization of norbornene/ethylene as well as CO/norbornene. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Geometrical and Linkage Isomers of [OsCl2(dmso)4] − The Complete Picture
Authors: Alessio Enzo , Serli Barbara , Zangrando Ennio , Calligaris Mario , Panina Natalia S. 
Published: August 2003

AbstractThe isomerisation between the three known isomers of the [OsCl2(dmso)4] complex — trans‐[OsCl2(dmso‐S)4] (1), cis,fac‐[OsCl2(dmso‐S)3(dmso‐O)] (2), and cis‐[OsCl2(dmso‐S)4] (3) — has been investigated by NMR spectroscopy, X‐ray crystallographic analysis, and DFT calculations. We show that the two dmso‐linkage isomers 2 and 3 equilibrate slowly at room temperature in solutions of both dimethyl sulfoxide (DMSO) and light‐protected chloroform. Although crystals of 2 precipitate from DMSO solutions, crystals of 3 were obtained from chloroform solutions. Compound 2 isomerises to 1 after exposure to sunlight, while 1 transforms into 2 in hot DMSO solution. The molecular energies were calculated by DFT methods, which show that in the gas phase there are small differences in the total energies (Et), with 1 exhibiting the lowest energy, in contrast with its low population in solution. This result indicates that the stability of each isomer in solution is not simply determined by Et, but that the solvent plays an important role. In fact, quantum chemical calculations for the isomerisation process 1 ⇄ 2 show a marked increase in the equilibrium constant with increasing the solvent polarity. The calculation of the metal−dmso binding energies, in combination with the X‐ray data, shows a significantly higher strength of Os−S bonds with respect to Ru−S bonds, which explains the different behaviour of otherwise analogous osmium−dmso and ruthenium−dmso complexes. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
The Substitution Reaction of (Chloro)bis(tetraisopropylcyclopentadienyl) Complexes of La, Pr, or Nd with Silylamides
Authors: Schmitt Oliver , Wolmershäuser Gotthelf , Sitzmann Helmut 
Published: August 2003

AbstractThe dimeric complexes [{(C5HR4)2Ln(μ‐Cl)(μ3‐Cl)Na(OEt2)}2] (1) (R = CHMe2, Ln = La, Pr, Nd) eliminate sodium chloride in toluene solution to form the (chloro)bis(cyclopentadienyl) complexes [(C5HR4)2LnCl] (2). Crystalline 2‐Nd contains monomeric molecules exhibiting two intramolecular Nd···CH3 interactions (Nd···C = 3.32 Å) with ring substituents. Reaction of complexes 1 with bis(trimethylsilyl)amides furnishes the tetranuclear complexes [{(C5HR4)2Ln(μ‐Cl)}2{NaN(SiMe3)2}2] (3) (R = CHMe2, Ln = La, Pr, Nd), which have been characterized by X‐ray crystal structure analyses. In solution the La2Na2 complex 3‐La eliminates NaC5HR4 (R = CHMe2) to form a mixture of 2‐La and [(C5HR4)La{N(SiMe3)2}2] (4). With less a bulky bis(dimethylsilyl)amide 1‐La yields the substitution product [(C5HR4)2LaN(SiHMe2)2] (5) (R = CHMe2). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
(4‐Acyl‐5‐pyrazolonato)titanium Derivatives: Oligomerization, Hydrolysis, Voltammetry, and DFT Study
Authors: Caruso Francesco , Massa Lou , Gindulyte Asta , Pettinari Claudio , Marchetti Fabio , Pettinari Riccardo , Ricciutelli Massimo , Costamagna Juan , Canales Juan Carlos , Tanski Joseph , Rossi Miriam 
Published: August 2003

AbstractTwenty 4‐acyl‐5‐pyrazolonato (Q) titanium derivatives of varied nuclearity have been synthesized from Ti(OR)4 or TiCl4 and characterized with spectroscopic methods (IR, NMR, ESI‐MS). While Ti−(β‐diketonato) cleavage is not seen in isolated solids, Ti−O(alkoxy) (or Ti−Cl) bonds cleave upon hydrolysis, leading to several structural forms, including oligomers. Ionic Q species with no Ti, i.e., obtained after Ti−Q cleavage, are seen for some Ti−Q derivatives by ESI‐MS, which also indicates a varied nuclearity for a given species, e.g., the isolated polynuclear [Q2Ti‐μ‐O]n has several “n” values. Mononuclear Ti complexes are obtained under rigorous anhydrous conditions. The cis structures of the mononuclear species (QT)2Ti(OCH3)2, QT = 3‐methyl‐4‐(neopentylcarbonyl)‐1‐phenylpyrazol‐5‐onato have been analyzed with DFT methods. A trans influence is a major driving force that accounts for several sets of Ti−O bonds. One of the cis stereoisomers is 56 kcal/mol higher in energy than the other two. In contrast, all (QT)2TiCl2 cis isomers show similar energies. Voltammetry of the mononuclear species (QT)2Ti(OnPr)2 and the antitumor tetranuclear compound [(QB)2Ti‐μ‐O]4, (QB = 4‐benzoyl‐3‐methyl‐1‐phenylpyrazol‐5‐onato) indicate that the TiIV is less prone to reduction to TiIII in the latter (Epc for the TiIV/TiIII couple is −1.71 V and −1.46 V versus Fc+/Fc, respectively). Potential antitumor compounds having a Ti/Q ratio of 1:1 do not disproportionate, unlike the equivalent acetylacetonato derivatives, and are water‐soluble. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Large‐Scale Synthesis of High Quality Trigonal Selenium Nanowires
Authors: An Changhua , Tang Kaibin , Liu Xianming , Qian Yitai 
Published: August 2003

AbstractA direct and simple one‐step hydrothermal reaction route has been developed for the synthesis of high quality trigonal selenium (t‐Se) nanowires at 110 °C, with (NH4)2S2O3 and Na2SeO3 as starting materials in the presence of the surfactant sodium dodecyl sulfate (SDS). The diameter of the trigonal selenium nanowires can be tuned by carefully adjusting the initial feedstock concentration. The unusual chain like structure of the target material plays a key role in determining the final morphologies of the products. Several factors, such as initial concentration of the feedstock, the presence of surfactant, and the temperature which influences the quality of the t‐Se nanowires, have been investigated. The optical properties of the t‐Se nanowires with different diameters were examined by means of UV/Vis absorbance spectroscopy at room temperature. The investigation revealed that the absorbance peak for the t‐Se nanowires with diameters of 20−40 nm shifts to the blue, relative to those for bulk t‐Se nanowires (374 nm) and nanowires with diameters of 50−130 nm (306 nm). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Polynuclear Nickel(II) Complexes: Preparation and Magnetic Properties of NiII4, NiII5, and NiII6 Species with Ligands containing O∩X∩O (X = S, Se or N) Donor Atoms
Authors: Paine Tapan K. , Rentschler Eva , Weyhermüller Thomas , Chaudhuri Phalguni 
Published: August 2003

AbstractA family of bisphenol‐containing ligands with XO2 donor atoms, where X = S, Se, or N, yields [NiII]4 (1) and (2), [NiII]5 (3), and [NiII]6 (4) complexes. Complex 2, 3, and 4 have been structurally characterised by X‐ray diffraction. The compounds were characterised spectroscopically and by variable‐temperature (2−295 K), variable‐field (1, 4, and 7 T) magnetic susceptibility measurements. Analysis of the magnetic data shows predominant ferromagnetic interactions between the nickel centres (SNi = 1) indicating “high‐spin” ground states for 1, 2, and 3, whereas complex 4 shows antiferromagnetic interactions. A plot of J vs. Ni−O−Ni angles for all structurally characterised Ni4O4 cubane cores, including 2, irrespective of their symmetry, shows a large variation of J values within a small range of Ni−O−Ni angles. A simple two‐J model was found to be adequate to describe the magnetic properties of the hexanuclear complex, 4. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Mononuclear Rhodium(I) Complexes with Chelating N‐Heterocyclic Carbene Ligands − Catalytic Activity for Intramolecular Hydroamination
Authors: Burling Suzanne , Field Leslie D. , Li Hsiu L. , Messerle Barbara A. , Turner Peter 
Published: August 2003

AbstractThe mononuclear cationic RhI complexes [Rh(cod)(mdd)]+X− and [Rh(CO)2(mdd)]+X− (X = BPh4, PF6) containing the chelating bidentate N‐heterocyclic carbene ligand 1,1′‐methylene‐3,3′‐dimethyldiimidazoline‐2,2′‐diylidene (mdd) have been synthesised and spectroscopically characterised. The complexes [Rh(cod)(mdd)]+BPh4− and [Rh(CO)2(mdd)]+PF6− have also been characterised by X‐ray crystallography. The dicarbonyl complexes catalyse the intramolecular hydroamination of 4‐pentyn‐1‐amine to 2‐methyl‐1‐pyrroline. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Synthesis, Kinetic Study and Molecular Orbital Investigation of Cadmium(II), Mercury(II) and Lead(II) Complexes with the Mixed Pendant‐Arm Macrocyclic Ligand 1,7‐Bis(carboxymethyl)‐4,10‐bis(1‐methylimidazol‐2‐ylmethyl)‐1,4,7,10‐tetraazacyclododecane
Authors: Di Vaira Massimo , Mani Fabrizio , Costantini Stefano Seniori , Stoppioni Piero , Vacca Alberto 
Published: August 2003

AbstractThe neutral [ML6]·3H2O complexes (M = CdII, HgII and PbII) formed with the potentially octadentate ligand 1,7‐bis(carboxymethyl)‐4,10‐bis(1‐methylimidazol‐2‐ylmethyl)‐1,4,7,10‐tetraazacyclododecane (H2L6) in its anionic deprotonated form, which bears two pairs of different dangling groups in trans positions on the cyclen skeleton, have been synthesized. Their low‐temperature limiting NMR spectra (1H and 13C) in D2O show that both the dangling groups and the ethylenic moieties of the macrocycle ring are in a fixed conformation in all complexes at 273 K. These conditions are relaxed at higher temperatures, yielding a dynamic behaviour that proceeds through both ring inversion and rearrangement of the pendant arms. The kinetic parameters for ring inversion have been obtained from the temperature‐dependent 13C NMR spectra. Cd: k(298 K) = 236 s−1; ΔH‡ = 72.9 ± 0.6 kJ·mol−1; ΔS‡ = 45 ± 2 J K−1·mol−1; Hg: k(298 K) = 292 s−1; ΔH‡ = 68 ± 3 kJ·mol−1; ΔS‡ = 29 ± 10 J K−1·mol−1; Pb: k(298 K) = 122 s−1; ΔH‡ = 65 ± 2 kJ·mol−1; ΔS‡ = 14 ± 5 J K−1·mol−1. In the absence of experimental structure determinations, some insight into the geometries has been obtained by quantum‐mechanical calculations. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
A Bulky Chelating Diamidoaluminum Monohydride − Synthesis, Structure and Reactions with Me3SnF and Heavy Group 16 Elements
Authors: Zhu Hongping , Chai Jianfang , Roesky Herbert W. , Noltemeyer Mathias , Schmidt Hans‐Georg , Vidovic Denis , Magull Jörg 
Published: August 2003

AbstractThe bulky chelating diamidoaluminum monohydride [ArN(CH2)3NAr]AlH(NMe3) (Ar = 2,6‐iPr2C6H3; 1) was prepared in excellent yield from the reaction of the diamine ArNH(CH2)3HNAr with a small excess of AlH3·NMe3 in toluene. Subsequent fluorination of 1 with Me3SnF resulted in the formation of the aluminum monofluoride [ArN(CH2)3NAr]AlF(NMe3) (2). Reaction of 1 with elemental E (E = S, Se and Te) proceeded in toluene with heating to yield the aluminum chalcogenides {[ArNH(CH2)3NAr]Al(μ‐E)}2 [E = S (3), Se (4), and Te (5)]. The structures of complexes 1, 2 and 4 have been determined by X‐ray diffraction analyses. Compounds 1 and 2 are well‐separated monomers with a central aluminum atom in a tetrahedral environment. The diamide ligand [ArN(CH2)3NAr]2− chelates the Al atom to form a distorted six‐membered AlN2C3 ring which features a boat conformation for 1 and a flattened chair conformation for 2. Compound 4, however, is a dimer with a central Al2Se2 core bearing an ideal four‐membered planar ring and two six‐membered AlN2C3 rings, both displaying a boat conformation. The latter two rings are arranged perpendicularly to the Al2Se2 core in a trans configuration. The IR spectra and 1H NMR spectroscopic data of compounds 3−5 suggest that the migration of the hydrogen from selenium to one of the nitrogens at the diamide ligand is involved in the course of the reaction. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Nanoparticulated Gold: Syntheses, Structures, Electronics, and Reactivities
Authors: Schmid Günter , Corain Benedetto 
Published: August 2003

AbstractThis microreview deals mainly with the synthesis and the electronic and chemical properties of gold nanoparticles. Modern synthetic routes, based on physical and on chemical procedures, as well as structural and optical features, are described. The bulk‐to‐molecule transition is discussed by studying size‐controlled quantum‐size effects, resulting in the determination of discrete electronic energy levels in Au55 clusters. Conductivity measurements of three‐ and two‐dimensionally organized ligand‐protected Au55 clusters are described, as well as the current techniques for the generation of ordered monolayers and artificial patterns of quantum dots. Finally, some aspects of the chemical activity of gold nanoparticles are discussed by considering ligand‐exchange processes and, last but not least, the expanding role of gold nanoparticles in catalysis is considered. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Synthesis, Structure and Reactivity of New Late Transition Metal Complexes Bearing Diphosphane Ligands Derived from Bis(pyrazol‐1‐yl)methane
Authors: Otero Antonio , Carrillo‐Hermosilla Fernando , Terreros Pilar , Expósito Teresa , Rojas Sergio , Fernández‐Baeza Juan , Antiñolo Antonio , López‐Solera Isabel 
Published: August 2003

AbstractModification of the multistep synthesis of the previously described bis[5‐(diphenylphosphanyl)pyrazol‐1‐yl)]methane (bppzm, 1) produces the novel diphosphane (diphenylphosphanyl)‐[5‐(diphenylphosphanyl)pyrazol‐1‐yl](pyrazol‐1‐yl)methane (p4m, 2). Treatment of this ligand with [MCl2(PhCN)2] (M = Pd, Pt) or [M(COD)(THF)2]BF4 (M = Rh, Ir) produces [MCl2(p4m)] (M = Pd 3, Pt 4) or [M(COD)(p4m)]BF4 (M = Rh 5, Ir 6) complexes, which chelate in a P,P‐bidentate fashion. Sulfidation of bppzm and p4m produces the disulfidophosphanes bppzmS2 (7) and p4mS2 (8). Treatment of 7 and 8 with [PdCl2(PhCN)2] produces [PdCl2(bppzmS2)] (9) and [PdCl2(pmS2)] (10), respectively, in which ligands 7 and 8 act in an N,N‐bidentate chelate fashion. In contrast, ligand 8 reacts with [Rh(COD)(THF)2]BF4 to produce [Rh(COD)(p4mS2)]BF4, where ligand 7 acts in a dynamic S,S‐chelate fashion. The activity of some of these complexes in the catalytic hydrogenation of olefins is reported and the single‐crystal X‐ray structures of 4, 8, and 9 have been obtained. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Partially Fluorinated Rare Earth Metal Complexes
Authors: Neculai Ana Mirela , Neculai Dante , Nikiforov Grigori B. , Roesky Herbert W. , Schlicker Christine , Herbst‐Irmer Regine , Magull Jörg , Noltemeyer Mathias 
Published: August 2003

AbstractThe reaction of LScBr2 (1), LYI2 (3), LHoI2 (4), or LErI2 (5) [L = N,N′′‐(1,3‐dimethyl‐1,3‐propanediylidene)bis(N′,N′‐diethyl‐1,2‐ethanediamine)] with Me3SnF was investigated. Treatment of 1 with Me3SnF results in the formation of (Me3BrSn‐μ‐F)2LSc (2) while compounds 3−5 give [LSnMe2][Me3SnI2] (6) as the only product that could be isolated and characterized. Metathesis reactions of 1 with AgSO3CF3 led to LSc(SO3CF3)2 (7). Compounds 1, 2, 6 and 7 were characterized by single‐crystal X‐ray structural analysis. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Monoarylated Fluoromesitylpalladium Complexes
Authors: Bartolomé Camino , Espinet Pablo , Martín‐Alvarez Jose M. , Villafañe Fernando 
Published: August 2003

AbstractMonoarylated complexes [PdCl(Fmes)(L‐L)] [Fmes = 2,4,6‐tris(trifluoromethyl)phenyl or fluoromesityl] and trans‐[PdCl(Fmes)L2] have been obtained by arylation of [PdCl2(L‐L)] (L‐L = tmeda) or trans‐[PdCl2L2] (L = SMe2), by splitting the bridging chloro ligands in [Pd(μ‐Cl)(Fmes)(NCMe)]2 {L‐L = 4,4′‐Me2bipy, biquinolyl (2,2′‐biquinoline), OPPhPy2‐N,N′, (OH)(CH3)CPy2‐N,N′, dppe, pte [1,2‐bis(phenylthio)ethane]; L = 4‐pic}, or by substitution of the diolefin in [PdCl(Fmes)(COD)] (L = tBuNC). A 1:1 ratio of [Pd(μ‐Cl)(Fmes)(NCMe)]2 and monodentate ligands affords [PdCl(Fmes)(NCMe)L] (L = 2,6‐lut, 3,5‐lut, PPh3), whereas a 1:1 mixture of [{PdCl(Fmes)(NCMe)}2(μ‐dppe)] and [PdCl(Fmes)(dppe)] is obtained with dppe under mild conditions. The precursor [Pd(μ‐Cl)(Fmes)(NCMe)]2 is generated by boiling under reflux [PdCl(Fmes)(COD)] in MeCN, and has been used to obtain various binuclear monoarylated complexes [Pd(Fmes)(μ‐X)L]2 [X = Br, L = MeCN, P(o‐Tol)3; X = Cl, L = CO, 4‐pic, 3,5‐lut, P(o‐Tol)3]. Other [Pd(Fmes)(μ‐X)L]2 complexes have been obtained from trans‐[PdCl(Fmes)(SMe2)2] (X = Cl, L = tht, SMe2, PPh3) and from K[Pd4(Fmes)4I5] [X = I, L = P(o‐Tol)3]. Despite the steric hindrance imposed by the Fmes ligand (ortho effect), the ligand‐substitution reactions are suggestive of associative mechanisms. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Synthesis, Structure and Chemical Transformations of Ethynylgermatranes
Authors: Lukevics Edmunds , Arsenyan Pavel , Belyakov Sergey , Pudova Olga 
Published: August 2003

AbstractEthynylgermatranes have been prepared from monosubstituted acetylenes by a three‐step synthesis without isolation of the hydrolytically unstable intermediate chlorogermanes and ethoxygermanes. Boiling an equimolar mixture of tetrachlorogermane Cl4Ge, acetylene RC≡CH and triethylamine in hexane leads to germylation of the Csp−H bond and the formation of ethynyl‐substituted trichlorogermanes. Subsequent alkoxylation of chlorogermanes by ethanol in the presence of triethylamine affords triethoxygermanes that then take part in transalkoxylation with triethanolamine to give ethynylgermatranes. The molecular structures of all ethynylgermatranes and the hexacarbonyldicobalt complex of 1‐heptynylgermatrane have been determined by X‐ray crystallography. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
1,2‐Bis‐N‐[2′‐(diphenylphosphanyl)benzoyl]diaminobenzene, a New Chelating Ligand with Versatile Coordination Properties
Authors: Burger Sylvain , Therrien Bruno , Süss‐Fink Georg 
Published: August 2003

Abstract1,2‐Bis‐N‐[2′‐(diphenylphosphanyl)benzoyl]diaminobenzene (dppbH; 1) was prepared by peptidic coupling and shown to exist, in the solid state, in the form of hydrogen‐bonded dimers by single‐crystal X‐ray structure analysis. As expected, 1 reacts with [MCl2(cod)] (M = Pd, Pt; cod = cyclooctadiene) to form square‐planar complexes. However, in the case of palladium [PdCl2(dppbH)] (2) is obtained, while in the case of platinum [Pt(dppb)] (3) is formed. Thus, the nature of the metal induces a completely different coordination mode: In 2, the dppbH ligand only coordinates through the two phosphorus atoms, while in 3 a dppb ligand, formed by deprotonation of the two amino functions in dppbH, coordinates through the two phosphorus atoms and through the two nitrogen atoms. The single‐crystal X‐ray analyses of the two square‐planar complexes reveal 2 to contain the two phosphorus atoms in a trans coordination mode and 3 to contain the two phosphorus atoms in a cis coordination mode. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Cover Picture: Heteronuclear Metal−Metal Contacts between Gold(I) and Group‐11, ‐12, and ‐13 Centers (Eur. J. Inorg. Chem. 17/2003)
Authors: Bardajía Manuel , Laguna Antonio 
Published: August 2003

AbstractThe cover picture shows a disc that contains a suspension of the complex [(C6F5)2Au{μ‐Ag(OClO3)}Au(C6F5)2] (solid) (Figure 1 in the Microreview) under ultraviolet light. The border of the disc is cooled with liquid nitrogen to a temperature close to 77 K and the centre of the disc is at room temperature. The luminescence and the colour of the complex changes from red (near 77 K), through orange and yellow, to green (room temperature). Details are discussed in the Microreview by M. Bardajía and A. Laguna on p. 3069 ff.