Structural studies on ruthenium(II) complexes used in interphase catalysis for the hydrogenation of ketones

Structural studies were performed on catalytically active ruthenium(II) complexes used in interphases, by means of XAFS spectroscopy. The EXAFS investigations indicate that the complexes retain their structural integrity when they are embedded on polysiloxane matrices to form stationary phase materials. The AXAFS studies reveal that the variations in the catalytic activity of the complexes with different ligands can be correlated to the differences in the electronic structure around the active ruthenium center. The EXAFS investigations show that, in asymmetric transfer hydrogenation reactions catalysed by ruthenium(II) complexes, the co‐catalyst plays a crucial role not only in enhancing the catalytic activity, but also in determining the structure of the intermediate species. Copyright © 2007 John Wiley & Sons, Ltd.     

Antimicorbial effects of newly synthesized organotin(IV) and organolead(IV) derivatives

Triorganotin(IV) and triorganolead(IV) derivatives of the types Me₃Sn(SCZ) and Ph₃Pb(SCZ) (where SCZ^? is the anion of a semicarbanzone ligand) have been synthesized by substitution reactions of trimethyltin chloride and triphenyl-lead chloride with semicarbazones derived from heterocyclic ketones. The resulting complexes have been characterized by elemental analyses, molecualr weight determinations and conductivity measurements. The mode of bonding has been established on the basis of infrared and ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopic studies. Some respresentative complexes have also been evaluated for their antimicrobial effects on different species of pathogenic fungi and bacteria; the results of these investigations have been reported in the present paper.     

Photoelectron spectroscopy of mono and binuclear iron and chromium cyclooctatetraene complexes

The ultraviolet photoelectron spectra of mono and binuclear cyclooctatetraene (COT) complexes (CO)₃FeCOT (I) [(CO)₃Fe]₂COT (II), CpCrCOT (Cp: 1,3 cyclopentadienyl) (III) and (CpCr)₂COT (IV) are reported. The interpretation of the low energy part of the spectra is followed by a discussion concerning the metal–ligand (COT) and metal–metal interactions. The calculated gas phase structure of CpCrCOT is presented and its main features are discussed.     

Experimental and computational studies of intracomplex reactions in Mg+(primary, secondary alkylamine) complexes induced by photoexcitation of Mg+

We report herein a comprehensive study of photoinduced reactions in complexes of Mg+ with primary (n-propyl- and isopropylamine) and secondary amines (dipropyl- and diisopropylamine) in the spectral range of 230-440 nm. Similar to the methyl- and ethylamine complexes studied previously, N-H bond activation of these complexes is very unfavorable. Instead, the C(alpha)-C, C-N, and C(alpha)-H bond-cleavage photoproducts are observed after photoexcitation of the Mg+ complexes (3(2)P<--3(2)S). For Mg+(primary amine) complexes, for example, Mg+-NH2CH2CH2CH3, and Mg+-NH2CH(CH3)2, the photoproducts resulting from C(alpha)--C rupture prevail after P(z) and charge-transfer excitations, whereas the Mg+ photofragment is predominant upon P(x,y) excitation. However, with further N-alkyl substitution, as in Mg+(secondary amine) complexes, for example, Mg+-NH(CH2CH2CH3)2 and Mg+-NH[CH(CH3)2]2, a novel intracomplex C-C coupling photoreaction dominates on P(x,y) excitation of Mg+, which is believed to arise from Mg+* insertion into the C-N bond. With P(z) and charge-transfer excitation, the Mg-R elimination photoproducts, arising from C(alpha)-C bond cleavage, predominate. The energetics and possible mechanisms of the intracomplex photoreactions are analyzed in detail with the help of extensive quantum mechanics calculations.     

Diels—Alder reaction. Effect of internal and external factors on the reactivity of diene—dienophile systems

The key factors influencing the Diels—Alder reaction rate at ambient and elevated pressures were elucidated using data on the reactivity of various diene—dienophile systems in usual and Lewis acid-catalyzed Diels—Alder reactions, the reaction enthalpy, complex formation, dissolution, and solvation, and the donor-acceptor properties of the reactants. It was found that taking account of both the orbital interaction energy and the balance of bond rupture and formation energies allows correct prediction of the reaction rate in the absence or in the presence of Lewis acids.     

Synthesis of naphthyridines and phenanthrolines using catalysts based on transition and rare-earth metals

Liquid-phase condensation of 3-, 4-, and 8-aminoquinolines with aliphatic and aromatic aldehydes catalyzed by transition and rare-earth metal complexes is an efficient method for synthesis of substituted 1,7- and 1,6-naphthyridines and 1,10-phenanthrolines.Institute of Organic Chemistry, Ural Branch, Russian Academy of Sciences, 450054 Ufa; Eastern Scientific-Research Institute of Coal Chemistry, 620219 Sverdlovsk. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1139–1148, May, 1992.     

Ion-exchange method for separation and concentration of platinum and palladium for analysis of environmental samples by inductively coupled plasma atomic emission spectrometry

An ion-exchange procedure is proposed for determination of Pt and Pd in environmental samples, using a Dowex 1-X10 anion-exchange resin. Pt and Pd were separated from the matrix elements in the sample by selective retention on the column as anionic chloro complexes and subsequent elution by circulated thiourea at 60 °C. The eluent, containing Pt and Pd was analyzed by inductively coupled plasma (ICP) atomic emission spectrometry (AES). Average recoveries of 98% and detection limit of 15 ng/g for both metals were achieved. Analysis of Pt and Pd concentrations in road dust, sampled from several sites in Germany was performed. The comparison of the obtained data with the concentrations of Pt and Pd in the same samples, determined by ICP-MS showed a very good agreement.     

Regio- and Stereocontrolled Nucleophilic Addition Reactions of An Unsymmetrically Disbustituted Butadiene η4-Molybdenum Cationic Complex

The reactions of a new cationic complex, [Cp(CO)₂Mo(η⁴-2-methyl-3-SPh-C₄H₄)]⁺ PF^?₆ (3), with carbon, hydride, and nitrogen nucleophiles were found to give only the C-1 addition products in good yield. The X-ray crystal structures of two of the addition products 4a and 4e confirm the regio- and stereochemistry of the nucleophilic additions.     

Concentrated electrolyte solutions at high temperatures and pressures

A survey is given of recent experimental results obtained from high-temperature, high-pressure investigations with water, aqueous solutions, and ionic fluids. Data on the static dielectric constant of water to 550°C and 5 kbar are given and discussed with respect to their relation to water structure. Infrared and Raman spectra of HDO in pure water have been obtained to 400°C and 4 kbar, which give information on hydrogen bonding. Xe–H₂O and CO₂–H₂O mixtures were investigated in the infrared. Ni(II) and Cu(II) complexes were investigated by absorption spectroscopy in aqueous solutions of high chloride content to 350°C and 2–6 kbar. The gas-liquid critical point of ammonium chloride was found at 880°C and 1635 bars. This fluid appears to be predominantly ionic even in the critical region. The possibility of converting pure polar fluids such as ammonia and water into concentrated ionic solutions by self-ionization at very high pressures is mentioned.This paper was presented at the symposium, The Physical Chemistry of Aqueous Systems, held at the University of Pittsburgh, Pittsburgh, Pennsylvania, June 12–14, 1972, in honor of the 70th birthday of Professor H. S. Frank.     

Synthesis and structural characterization of novel bridged platinum(II) biscarbene complexes

Novel bridged platinum(II) biscarbene complexes are reported: 1,1′-dimethyl-3,3′-methylene-4-diimidazolin-2,2′-diylidene platinum(II) (3) and 1,1′-dimethyl-3,3′-ethylene-4-diimidazolin-2,2′-diylidene platinum(II) complexes 4 are directly accessible in high yields starting from platinum halides. The one-pot synthesis obviates the need for multi-step reactions via metal precursors or free carbenes. An X-ray crystal structure of 1,1′-dimethyl-3,3′-methylene-4-diimidazolin-2,2′-diylidene platinum(II) dibromide (3b) confirmed the structural similarity to the known corresponding palladium complexes. Since free 1,1′-di-R-3,3′-methylene-4-diimidazolin-2,2′-diylidenes are only available in low yields this synthetic route provides an easy access to the corresponding carbene complexes.