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141.
Helmut Schwarz Wolfgang Mathar Ferdinand Bohlmann 《Journal of mass spectrometry : JMS》1974,9(1):84-87
The methyl cleavage from piperidides of type CH3(CH?CH)nCONC5H10 with n = 1 to 3 does not proceed via ring contraction as shown earlier with n = 0. The fragmentation can be formulated with the concept of neighbouring group participation of the amide function which leads to a cyclic transition state. Investigations with a 2H-labelled compound in the case of n = 1 as well as energy measurements (AP, IP, Ek) agree with this assumption. 相似文献
142.
The synthesis of chiral 12-phenyi(2H)dodecanoic acids as metabolic probes for the evaluation of the stereo-chemical course of the biosynthesis of 1-alkerses from fatty acids in plants and insects is described. The diastereoisomeric (2R, 3R)- or (2S, 3S)-12-phenyl(2,3?2H2)dodecanoic acids 11 are obtained in high chemical and optical yield (>97% e.e.) from the readily available (E)-12-phenyl(2,3-2H2)dodec-2-enoic acid ( 10 ) or (E)-12-phenyldodec-2-enoic acid ( 10a ) by microbial reduction with wet packed cells of Clostridium tyrobutyricum in either 2H2O or H2O buffer. (2R)- and (2S)-12-phenyl(2?2H)dodecanoic acids 9 (>97% e.e.) are accessible from the allylic alcohol 6 via Sharpless epoxidation with (+)-L- or (?)-D-diethyl tartrate, Synthetic routes to the (E)- and (Z)-11-phenyl(1?2H) undec-1-enes 16 and 16a as reference compounds are also included. 相似文献
143.
The coordinative properties of the acceptor ligand CS are discussed on the basis of the new thiocarbonyl complexes CpCr(CO)(CS)(NO) (I), [CpCr(CS)(NO)2]PF6 (II), CpCr(CS)(L)(NO) (L = pyridine (III) or trimethylphosphane (IV) and related carbonyl complexes. The IR and NMR spectra (1H, 13C, 31P) of the complexes indicate ligand—ligand interactions between CS and both the nitrosyl group and the cyclopentadienyl ring. An attempt is made to compare CS with other sulphur-containing acceptor ligands such as NS (in CpCr(CO)2(NS)) and CS2 (in CpCr(CS2)(PMe3)(NO)). 相似文献
144.
145.
Joseph Schwarz Detlef Schrder Helmut Schwarz Christoph Heinemann Jan Hruk 《Helvetica chimica acta》1996,79(4):1110-1120
State-of-the-art ab initio studies demonstrate that the reaction Pd+ + CH3I → PdCH2I+ + H. is endothermic by ca. 20 kcal/mol, which translates into a bond dissociation energy (BDE) of ca. 83 kcal/mol for the Pd+? CH2I bond. This figure is in agreement with an experimental bracket of 68 kcal/mol < BDE(Pd+? CH2I) < 92 kcal/mol. Based on these findings, the previously studied Pd+/CH3I system was re-investigated, and double-resonance experiments demonstrate that the formation of PdCH2I+ occurs stepwise via PdCH as a reactive intermediate. Further, ion/molecule reactions of PdCH2I+ with unsaturated hydrocarbons are studied, which reveal the formation of carbon–carbon bonds in the gas phase. 相似文献
146.
Bis(cyclopentadienyl)methane-bridged Dinuclear Complexes, V[1]. – Heteronuclear Co/Rh-, Co/Ir-, Rh/Ir-, and Ti/Ir Complexes with the Bis(cyclopentadienyl)methane Dianion as Bridging Ligand* The lithium and sodium salts of the [C5H5CH2C5H4]- anion, 1 and 2 , react with [Co(CO)4I], [Rh(CO)2Cl]2, and [Ir(CO)3Cl]n to give predominantly the mononuclear complexes [(C5H5-CH2C5H4)M(CO)2] ( 3, 5, 7 ) together with small amounts of the dinuclear compounds [CH2(C5H4)2][M(CO)2]2 ( 4, 6, 8 ). The 1H- and 13C-NMR spectra of 3, 5 , and 7 prove that the CH2C5H5 substituent is linked to the π-bonded ring in two isomeric forms. Metalation of 5 and 7 with nBuLi affords the lithiated derivatives 9 and 10 from which on reaction with [Co(CO)4I], [Rh(CO)2Cl]2, and [C5H5TiCl3] the heteronuclear complexes [CH2(C5H4)2][M(CO)2][M′(CO)2] ( 11–13 ) and [CH2(C5H4)2]-[Ir(CO)2][C5H5TiCl2] ( 17 ) are obtained. Photolysis of 11 and 12 leads almost quantitatively to the formation of the CO-bridged compounds [CH2(C5H4)2][M(CO)(μ-CO)M′(CO)] ( 14, 15 ). According to an X-ray crystal structure analysis the Co/Rh complex 14 is isostructural to [CH2(C5H4)2][Rh2(CO)2(μ-CO)] ( 16 ). 相似文献
147.
Jerzy Mroziński Jiří Kohout Mária Hvastijová Helmut Köhler 《Transition Metal Chemistry》1986,11(12):481-484
Summary New coligand isomers of composition Cu{N(CN)2}2(pz)2 and Cu{pz · N(CN)2}2 (pz = pyrazole) were prepared and studied by measuring their magnetic susceptibilities up to 4.2K and by aid of their e.s.r., ligand field and i.r. spectra. The susceptibility data have been analysed with various models for the exchange-coupled copper(II) polymers. It is shown that the resultant exchange coupling is ferromagnetic for Cu{N(CN)2}2(pz)2 (J 1.1 - 1.4 cm–1) but antiferromagnetic for Cu{pz · N(CN)2}2 (J –0.4 cm–1). A polymeric chain structure is proposed for Cu{N(CN)2}2(pz)2 havingpseudo-octahedrally coordinated copper(II) and CN-bridging dicyanamide ligands. Its coligand isomer contains anionic chelate ligands, formed by nucleophilic addition between N(CN)2 and pz in the copper(II) coordination sphere, and giving with this central atom a square-planar system. Definite, but slight axial interaction takes place between these structure units. 相似文献
148.
Helmut Bode und Wolfgang Arnswald 《Fresenius' Journal of Analytical Chemistry》1962,185(3):179-201
Zusammenfassung Es wird das Verhalten der Elemente Cu, Ag, Au, Zn, Cd, Hg, In, Tl, Ge, Sn, Pb, As, Sb, Bi, Se, Te, Mo, W, Re, Ru, Rh, Pd, Os, Ir, Pt bei der Extraktion mit CCl4 in Anwesenheit von Na-Diäthyl-DTP beschrieben. Die Untersuchungen wurden in 0,1–10 n salzsauren und 0,1–15 n schwefelsauren Lösungen durchgeführt. Die Eigenschaften derjenigen Diäthyl-DTP-Verbindungen, die in dieser Arbeit unberücksichtigt blieben, wurden an Hand der Literatur so weit beschrieben, wie es für Extraktionen von Bedeutung sein kann. Das teilweise recht unterschiedliche Verhalten der einzelnen Elemente, sowie in einigen Fällen auch der verschiedenen Wertigkeitsstufen eines Elementes lassen die Möglichkeit für eine größere Anzahl analytischer Trennungen erkennen. In vielen Fällen sind auch photometrische Bestimmungen möglich.Unsere Arbeit wurde durch Gaben der Deutschen Forschungsgemeinschaft und des Verbandes der chemischen Industrie — Fonds der Chemie — gefördert, wofür auch an dieser Stelle gedankt sei.I. Mitteilung: Bode, H. und W. Arnswald: diese Z. 185, 99 (1962). 相似文献
149.
René Csuk Johannes Haas Helmut Hönig Hans Weidmann 《Monatshefte für Chemie / Chemical Monthly》1981,112(6-7):879-882
A synthesis of new boron containingMannich bases of salicylamide by reaction of salicylamide, formaldehyde and boron-heterocycles is reported.
VIII. Mitteilung:Stump, R. K., Zimmerman jr., H. K., Schleppnik, A. A., Gutsche, C. D., Liebigs Ann. Chem.667, 18 (1963). 相似文献
150.
Hella Folkerts Kurt Dehnicke Jrg Magull Helmut Goesmann Dieter Fenske 《无机化学与普通化学杂志》1994,620(7):1301-1306
Phosphorane Iminato-Trichloroselenates(II): Syntheses and Crystal Structures of [SeCl(NPPh3)2]+SeCl3? and [Me3SiN(H)PMe3]2+[Se2Cl6]2? [SeCl(NPPh3)2]+SeCl3? has been synthesized by the reaction of Se2Cl2 with Me3SiNPPh3 in acetonitrile solution, forming orangered crystals, whereas red crystals of [Me3SiN(H)PMe3]2+[Se2Cl6]2? were obtained by the reaction of Me3SiNPMe3 with SeOCl2 in acetonitrile solution. Both complexes were characterized by X-ray structure determinations. [SeCl(NPPh3)2]+SeCl3?: Space group P21/n, Z = 4, structure solution with 7 489 observed unique reflections, R = 0.057. Lattice dimensions at ?60°C: a = 1 117.0; b = 2 241, c = 1 407.5 pm, β = 95.61°. In the cation [SeCl(NPPh3)2]+ the selenium atom is φ-tetrahedrally coordinated by the chlorine atom and by the nitrogen atoms of the phosphorane iminato ligands, whereas the anion SeCl3? has a T-shaped structure with φ-trigonal-bipyramidale surrounding of the selenium atom. [Me3SiN(H)PMe3]2+[Se2Cl6]2?: Space group P21/c, Z = 4, structure solution with 2 093 observed unique reflections, R = 0.080. Lattice dimensions at ?70°C: a = 956, b = 828, c = 1 973 pm, β = 93.80°. The structure consists of [Me3SiN(H)PMe3]+ ions and planar [Se2Cl6]2? anions, in which the selenium atoms are bridged nearly symmetrically by two chlorine atoms. 相似文献