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11.
The kinetics of the reaction between organocobaloximes, RCo(DH)2H2O, and iodine have been investigated. They reveal the participation of an RCo(DH)2H2O · I2 intermediate which undergoes intramolecular transalkylation and acts as an electrophile towards a second organocobaloxime molecule. The trend in reactivity as the R group is varied is discussed. 相似文献
12.
Molecular mechanics calculations on cycloheptadiene indicate that the molecule has a structure which undergoes a wide pseudorotational motion between two C1 forms, and a C1 form, and this structure is in equilibrium with the C2 form. It is shown that this equilibrium mixture is consistent with all of the available experimental data. 相似文献
13.
14.
Studies of the preparation of 1,8-dihydroazocines and transannular cyclization of hydroazocines to produce functionalized pyrrolizidines are described. Results are presented which demonstrate that unsymmetrically substituted acetylenes bearing at least one electron withdrawing groups undergo efficient cycloaddition to 1 - β - styryl - 1,2 - dihydropyridine producing in a regio-selective fashion 3,4 - disubstituted - 1,8 - dihydroazocines. The dihydroazocines generated in this manner can be converted to 1 - formyl - Δ4,5 - epoxyazocines which undergo interesting rearrangement reactions to form pyrrolizidines when subjected to methoxide deformylation followed by acid treatment. In addition, 1,6,7,8 - tetrahydroazocines can be converted to pyrrolizidines under bromination conditions. The intriguing chemical process which occur under the conditions outlined above are described. 相似文献
15.
Michael Stavola J.M. Friedman R.A. Stepnoski Mark G. Sceats 《Chemical physics letters》1981,80(1):192-194
Cooperative vibronic spectra involving Gd3+ electronic transitions and the vibrational transitions of nearby water molecules are used to determine the stretching spectrum for isotopically dilute OH in a solution of GdCl3 in D2O. The OH stretching spectrum of water molecules in the first hydration sphere is shifted to lower energy than that of the bulk liquid. 相似文献
16.
Ingemar Wadsö 《Thermochimica Acta》1985,96(2):313-325
The field of isothermal microcalorimetry as applied to systems of interest for aqueous solution chemistry, biochemistry and in cellular biology is briefly reviewed. Some techniques recently developed in the author's laboratory are described. 相似文献
17.
Robert G. Behrens 《Journal of organometallic chemistry》1976,121(3):C63-C65
The results of low temperature heat capacity studies on Mn2(CO)10(s) and Re2(CO)10(s) are compared with literature reports. It is shown that the values of vaporization enthalpies and entropies correspond with those of the low temperature stable phase. 相似文献
18.
Kikuo Miyokawa Masayuki Itoh Takummi Etoh Setsuko Kinoshita Isao Masuda 《Thermochimica Acta》1985,96(1):227-234
Kinetic and thermodynamic aspects of the axial base dissociation of solid Co(salen) (X-py) complexes, X = H (1), 3-Me (2), 4-Me (3), 3,4-Me2 (4), 3,5-Me2 (5), 3-NH2 (6), 3-Cl (7), 3-CN (8), 4-CN (9), have been investigated by means of TG-DSC and isothermal weight-loss measurements. These adducts endothermically dissociate the axial base giving rise to the oxygen-active Co(salen) complex. The axial base dissociation reactions fit the contracting disc equation and the kinetic compensation effect is observed for all the adducts excepting Adducts 4–6. For the remaining adducts the kinetic and thermodynamic stabilities of the Co-(X-py) bond are found to increase linearly with increasing Hammett's substitution constants of X except for Adducts 3 and 9. These results are discussed in terms of the σ and π interactions between cobalt(II) and substituted pyridine. Factors dominating the kinetic bond stability are briefly discussed. 相似文献
19.
The title compound, Cu(S2CNEt2)2, behaves at low temperatures (1–20 K) as a normal spin-1/2 molecule, with 〈g〉 =2.06 and the Curie-Weiss θ = +0.25 K. This result contradicts an earlier investigation that led to the suggestion that the crystallographically-occurring dimers are coupled ferromagnetically. 相似文献
20.
S.D. Christian J. Grundnes P. Klaeboe C.J. Nielsen T. Woldbaek 《Journal of Molecular Structure》1976,34(1):33-45
The infrared spectra of 1,1,2-trichloroethane were recorded from 4000 to 50 cm?1 in the vapour and liquid states. Additional spectra above 200 cm?1 of the low temperature crystal and of two crystalline solids, prepared by compressing the sample in a diamond anvil cell, were obtained. Also, infrared spectra of the liquid and of the compound dissolved in CS2 were recorded at increased pressures. Raman spectral data of the liquid (including polarization measurements) and of the low temperature crystal were obtained.The fundamental frequencies for each of the two conformers, C1 and Cs, were assigned and the results checked by normal coordinate analysis. The same diagonal and off-diagonal force constants were employed for the two conformers and the force fields were derived by means of a least squares refinement, including data for chloroethane, 1,1-dichloroethane and various deuterated species. A standard deviation of 3 % was obtained in the final fit.From the changes in relative intensities for infrared bands belonging to the C1 and Cs conformers with increasing pressure, the volume differences (ΔV¯between the conformers were determined in CS2 solution and in the pure liquid. 相似文献