Tetramethyldisilan-1,2-diyl-verbrückte Dicyclopentadienyl-und Diindenylmetalldichloride der 4. Gruppe – Kristallstruktur von

Tetramethyldisilane-1,2-diyl bridged Dicyclopentadienyl and Diindenyl Metal Dichlorides of the Group 4 Metals – Crystal Structure of Dicyclopentadienyl and diindenyl metal dichlorides of the type Cp′? SiMe₂SiMe₂? Cp′MCl₂ (Cp′ = C₅H₄, M = Ti ( 1 ), Zr ( 2 ), Hf ( 3 ); Cp′ = C₉H₇, M = Zr ( 4 ), Hf ( 5 )) were synthesized and characterized by means of their ¹H, ¹³C, ²⁹Si-n.m.r., MS, and IR spectra. The crystal structure of 2 was determined.     

Sulfide oxygenation by tert-butyl hydroperoxide with mononuclear (Me3TACN)Mn catalysts

Mononuclear (Me₃TACN)MnX₃ compounds, where X is Cl⁻, Br⁻, or N₃⁻, and Me₃TACN is 1,4,7-N,N′,N″-trimethyl-1,4,7-triazacyclononane, have been tested for catalyzing both sulfide oxygenation and styrene epoxidation by tert-butyl hydroperoxide (TBHP) and display turnover frequencies (TOF) up to 200 h⁻¹ at room temperature. Sulfoxides or sulfones may be produced selectively by varying reaction conditions. Product distribution from the oxygenation reactions of ethyl phenyl sulfide, 2-chloroethyl phenyl sulfide, and styrene is consistent with a mechanism involving an early single-electron transfer (SET) step.     

Remarkable reactivity enhancement with Sb?N inter-coordination of ethynyl-1,5-azastibocines in Pd-catalyzed cross-coupling reactions with organic halides

The reaction of 12-arylethynyl-6-methyl-5,6,7,12-tetrahydrodibenzo[c,f][1,5]-azastibocines with organic halides such as acyl halides and aryl halides in the presence of PdCl₂(PPh₃)₂ as a catalyst led to the formation of cross-coupling products, alkynyl ketones and diaryl acetylenes, in good yields. The reactivity of the ethynyl group on the 1,5-azastibocines was far superior to that on diphenyl(phenylethynyl)stibane, which brought about marked improvement in the reaction conditions (lower temperature and shorter reaction time) and in the yields of the cross-coupling products. Single-crystal X-ray analysis of the ethynyl-1,5-azastibocine showed the presence of intramolecular Sb?N interaction which should be responsible for the remarkable reactivity enhancement of the 1,5-azastibocines for this type of reaction.     

Dawson结构钼钒磷杂多化合物对苯酚过氧化氢羟化作用的研究

Ｄａｗｓｏｎ结构钼钒磷杂多化合物对苯酚过氧化氢羟化作用的研究于剑锋，杨宇，吴通好，孙家锺（吉林大学化学系理论化学研究所，长春，１３００２３）关键词Ｄａｗｓｏｎ结构钼钒磷杂多化合物，苯酚羟化，过氧化氢苯二酚（ＤＢＨ）是重要的化工原料．由芳香化合物羟化制...     

Synthesis of 4-arylcarbamoyl-5-(2-hydroxynaphthylazo)imidazoles and 1-substituted naphtho[2,1-e]imidazo[5,1-c][1,2,4]triazines

The reactions of β-naphthol with 5-diazoimidazoles and imidazolyl-5-diazonium salts containing chemically different carboxamide groups in position 4 were studied. Heterocyclization of 4-arylcarbamoyl-5-(2-hydroxynaphthylazo)imidazoles formed in these reactions was investigated. The presence of the NH fragment in the amide group prevents this process, the reaction giving instead 3-substituted 3,7-dihydroimidazo[4,5-d][1,2,3]triazin-4-ones, which is due to reversibility of C-azo coupling. Methods for modification of 1-ethoxycarbonyl group in the naphtho[2,1-e]imidazo[5,1-c][1,2,4]triazine system were developed and used to prepare substituted carboxamides inaccessible by other routes. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1208–1213, July, 2006.     

Applicability of glass fiber as a support material for generation of gaseous standard mixtures using thermal decomposition of the surface compound. Calibration of analytical equipment

The use of glass fiber as a support material for a surface compound serving to generate gaseous standard mixtures of ethene is described. The technique is based on the process of thermal decomposition of the surface compound in a desorber connected on‐line via a multi‐port valve to the calibrated device. The surface compound undergoes thermal decomposition at 245°C, yielding known amounts of ethene. The method enables on‐line preparation of a standard mixture immediately before the calibration step. Consequently, it can be also applied for the generation of standard mixtures containing volatile, malodorous, unstable, and toxic compounds.     

Synthesis and Structures of Titanosiloxane Cage Compounds

Reaction of (triphenylmethyl)silanetriol (1) with cyclopentadienyltitanium trichloride (CpTiCl₃) in the presence of triethylamine as a HCl scavenger gave both compounds of a partial open-cage type {[Ph₃CSiO(OH)]₃(Ph₃CSiO_3/2)(CpTiO_3/2)₄} (2) and cube type (Ph₃CSiO_3/2CpTiO_3/2)₄ (3). The 1:1 reaction of 1 and CpTiCl₃ in toluene solvent at reflux temperature for 3 d afforded compounds 2 (22%) and 3 (36%). When 1 is reacted with a 1.5 fold excess of CpTiCl₃ under the same conditions, compound 3 was obtained in high yield (81%) along with 2 in trace quantities. Compounds 2 and 3 were fully characterized by the analyses of ¹H, ¹³C, ²⁹Si NMR, IR, and FAB MS data. The solid-state structure of 3 was determined by a single crystal X-ray diffraction study. Compound 3 had shown to have catalytic activity for the oxidation of alkenes such as 1-octene, cyclooctene, and norbornene with t-butyl hydrogen peroxide. The effect of solvent was observed in this epoxidation reaction. The order of reactivity were decreased as follows: CHCl₃ > hexane THF.     

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.     

镧系元素的双—（9—钨—2—钼磷）杂多酸钾的合成与性质研究

自1971年Peacock等首次合成出以杂多阴离子为配位体的镧系元素的一些杂多配合物[Ln(XW_(11)O_(39))_2]~(n-)(X=P,Si)以来,Zuhairi等又合成出镧的一些其它杂多钨酸盐[La(XW_(11)O_(39))_2]~(n-)(X=B,Si,Ge,P,As)。 为开发新型的镧系元素催化剂,我们系统地研究了镧系元素的杂多钨酸盐和杂多钼酸盐。本文报道有关K_(11)[Ln(PW_9Mo_2O_(39))_2]·nH_2O(Ln=La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Er,Yb)的合成及性质的研究结果。