摘要:

AbstractOxidation ofN,N‐di‐n‐butyldithiocarbamato (bu2dtc) complexes of Cu(I), Ni(II), Zn(II), Cd(II) and Hg(II) is reported. Oxidation of Ni(bu2dtc)2with Cl2, Br2, or of NiX2(X = Cl, Br, NO3) withN,N,N′,N′‐tetra‐n‐butylthiuram disulfide (bu4tds) gives complexes of composition [Ni(bu2dtc)3]X. These compounds are diamagnetic and dissolve in nitrobenzene as 1:1 electrolytes, their UV spectra resemble that of the iso‐electronic Co(bu2dtc)3. The experimental data are in accord with the assumption that in these compounds Ni(IV) flow spind6) is surrounded by 6Satoms in octahedral symmetry. The analogous selenium compound tris (N, N‐di‐n‐butyldiselenocarbamato) nickel(IV) bromide, having the same properties as the thio compounds, can also be prepared. Oxidation of Cu(bu2dtc) with Cl2or Br2yields paramagnetic products with the composition CuX3(bu2dtc), in which Cu also has the formal oxidation number + 4, but the structure of these compounds is still obscure. Oxidation of Zn(bu2dtc)2and the corresponding Cd and Hg compounds yields products, the analysis of which suggests the composition MX2(bu2dtc)2(M = Zn, Cd or Hg, X = Br or I), but infrared studies indicate that the dithiocarbamato ligands of the starting substances are oxidized to bu4tds, which in the reaction products is coordinated to the metal in its nor

ISSN:0165-0513    

DOI:10.1002/recl.19690880602

出版商:WILEY‐VCH Verlag    

年代:1969

数据来源: WILEY

摘要:

AbstractThe synthesis of the α‐diazosulfonesm‐XC6H4SO2CHN2(X = CH3O, CH3, Cl, CF3and NO2) by the method ofvan LeusenandStratingis described. The pseudo first order rate constants for the acid‐catalysed hydrolysis of these a‐diazosulfones and those ofp‐XC6H4SO2CHN2(X = CH3O, CH3, H, Cl, NO2) in 40% (v/v) dioxane‐water at 25° have been correlated by theHammettqσ equation. The deviation found for thep‐CH3O‐derivative is discussed. A linear correlation has been found between the logarithm of the rate constants and the frequencies of the infrared absorption of the diazo group at about 2100 cm−1. This relationship between rate data and infrared frequencies can be extended to the acid‐catalysed solvolysis of other types of ali

ISSN:0165-0513    

DOI:10.1002/recl.19690880603

出版商:WILEY‐VCH Verlag    

年代:1969

数据来源: WILEY

摘要:

AbstractTwenty new compounds of the general formula M(CH3CN)mn+(anion)n−are described. In this formula M = (C2H5)4N, Li, Mg, Ca, Mn, Fe, Co, Ni, Cu, and Zn, n = 1 or 2, m = 0‐8, and the anions are (HgpCl2p+q)q−, in which p = 1‐5 and q = 1 or 2.These compounds are prepared by chloride‐ion transfer reactions between MClnand HgCl2in acetonitrile. The process is followed conductometrically for some cases.The compounds are identified and characterized by chemical analyses, ligand‐field spectra, infrared spectra, and Raman spectra. Both tetrahedral and linear coordinated chloromercurate(II) anions are found to be present in the soli

ISSN:0165-0513    

DOI:10.1002/recl.19690880604

出版商:WILEY‐VCH Verlag    

年代:1969

数据来源: WILEY

摘要:

AbstractThe infrared absorption and Raman spectra of the compounds KNO2S2O7and NOHS2O7have been studied. It follows from these spectra that both compounds are ionic and should be written as K+NO2+S2O7−and NO+HS2O7−, respectiv

ISSN:0165-0513    

DOI:10.1002/recl.19690880605

出版商:WILEY‐VCH Verlag    

年代:1969

数据来源: WILEY

ISSN:0165-0513    

DOI:10.1002/recl.19690880606

出版商:WILEY‐VCH Verlag    

年代:1969

数据来源: WILEY

摘要:

AbstractVarious methods of selective degradation of [14C]‐cyclopentene, [14C]‐cyclohexene and [14C]‐cycloheptene are described, which render it possible to determine the specific activity of each ring carbon atom. The synthesis of [1‐14C]‐cycloheptene from [l‐14C]‐cyclohexanone

ISSN:0165-0513    

DOI:10.1002/recl.19690880607

出版商:WILEY‐VCH Verlag    

年代:1969

数据来源: WILEY

摘要:

AbstractThe double bond migration of [l‐14C]‐cyclohexene under the influence of potassiumtert‐butoxide in dimethyl sulfoxide has been studied at three temperatures. The activation parameters are ΔH‡ = 19.5 ± 0.4 kcal/mole and ΔS‡ = −24.6 ±0.6 e.u.The reaction is first order in olefin and 3/2 order in base up to about 0.3 molar. It is postulated that in dimethyl sulfoxide a small amount of base is present as a catalytically ineffective trimer, which dissociates into various active basic species, thus explaining the 3/2 order. At concentrations above 0.3 molar the kinetic order decreases, presumably because of ineffective solvation of charged species by lack of so

ISSN:0165-0513    

DOI:10.1002/recl.19690880608

出版商:WILEY‐VCH Verlag    

年代:1969

数据来源: WILEY

摘要:

AbstractThe base‐catalyzed double bond migration of [14C]‐cyclopentene and [1‐14C]‐cycloheptene has been studied in a solution of potassiumtert‐butoxide in dimethyl sulfoxide at three temperatures. The activation parameters for cyclopentene are ΔH‡ = 22.1 ± 1.6 kcal/mole and ΔS‡ = ‐23.3 ± 2.6 e.u. and for cycloheptene ΔH‡ = 18.3 ± 0.5 kcal/mole and ΔS‡ = −24.5 ±0.8 e.u. It has been found that the isomerization rate increases with increasing ring size. This result is discussed in terms of angles between the planes formed by the bonds H‐C(allyl)‐C(olef.) and t

ISSN:0165-0513    

DOI:10.1002/recl.19690880609

出版商:WILEY‐VCH Verlag    

年代:1969

数据来源: WILEY

摘要:

AbstractA kinetic investigation is reported of the potassiumtert‐butoxide catalyzed isomerization of methyl linoleate intert‐butanol and mixtures oftert‐butanol and ethylene glycol dimethyl ethers.The product is a mixture of 9cis, 11transand 10trans, 12cismethyl octadienoates.The reaction is first order in olefin and 1.5 order in base over the entire range of base concentrations (0.05 to 1M).The order in base and the acceleration of the reaction by addition of ethylene glycol dimethyl ethers are disc

ISSN:0165-0513    

DOI:10.1002/recl.19690880610

出版商:WILEY‐VCH Verlag    

年代:1969

数据来源: WILEY

摘要:

AbstractThe reduction of aliphatic carbonium ions to alkanes with molecular hydrogen is reported. A kinetic study of this reaction has been made in the two‐phase solvent system HFFreon 113. The following parameters were investigated: temperature, hydrogen pressure, deuterium isotope effect and structure of the carbonium ion.The kinetics of the reverse reaction ‐ formation of carbonium ions from alkanes and protons in the system HF‐SbF5‐ were studied for the case of trimethylcarbonium ion. From the equilibrium constant an upper limit for the basicity of isobutene has been c

ISSN:0165-0513    

DOI:10.1002/recl.19690880611

出版商:WILEY‐VCH Verlag    

年代:1969

数据来源: WILEY