摘要:

The crystal structure of a thiathiophthen nitrogen isostere (7) has been solved by X-ray analysis. The crystal belongs to the triclinic system with unit cell dimensions:a = 11.275(11),b = 9.558(10),c = 10.797(10) Å, α = 92.50(10), β = 116.98(10), γ = 92.61(10)°. There are two molecules per unit cell, space group. The data were collected by diffractometer with CuKα radiation. The structure was solved by symbolic addition procedures, and fully refined anisotropically using full-matrix least squares to anRfactor of 6.3%.The S—S and S—N bond lengths were found to be 2.364 and 1.887 Å, respectively. This reveals the partial bonding character between S … S … N atoms.

ISSN:0008-4042    

DOI:10.1139/v71-029

出版商:NRC Research Press    

年代:1971

数据来源: NRC

摘要:

A quantitative interpretation of the extractive distribution of cadmium chelates of TAR (= H2A) between liquid organic and water phases has been made and two groups of extractable species have been determined: (a) uncharged complexes of the type CdA in which co-ordinated water is replaced by suitable uncharged organic base (2,9-dimethyl-1,10-phenanthroline) and (b) charged complexes CdA22−which are extracted as ionic pairs in the presence of charged organic bases.The evaluation of the character of the bases and the effect of pHand the nature and concentration of other inorganic anions are presented.

ISSN:0008-4042    

DOI:10.1139/v71-030

出版商:NRC Research Press    

年代:1971

数据来源: NRC

摘要:

The rate and mechanism of transfer of oxygen between thiosulfate ion and water, in the presence of sulfite, has been investigated with18O-enriched Na2S2O3. The principal path, for the conditions examined, is via sulfur atom transfer between sulfite and thiosulfate, accompanied by oxygen atom transfer between sulfite and the solvent water. The latter path is suppressed at high pH, and oxygen transfer from thiosulfate proceeds to the sulfite stage only. At intermediate pH, the two processes have comparable rates, and the kinetics show the behavior expected for a system of consecutive, reversible first order processes. Under these conditions sulfite is observed to behave as a true intermediate, first accumulating18O from thiosulfate, and then releasing it to the solvent water.

ISSN:0008-4042    

DOI:10.1139/v71-031

出版商:NRC Research Press    

年代:1971

数据来源: NRC

摘要:

The value ofG(D2) from the radiolysis of gaseous DCl is 7.4 ± 0.3 at dose rates of 1015and 1027 Ev g−1 s−1. The yield of hydrogen (D2, H2, or HD) from electron reactions and the unscavengeable yield are, within experimental error, the same as in HCl. However, fewer thermal hydrogen atoms are formed in primary processes and a greater proportion of the electrons produce clustered negative ions ((DCl)−(c)) than in HCl. The magnitude ofat 288 K is a factor of three smaller thanat the same temperature.

ISSN:0008-4042    

DOI:10.1139/v71-032

出版商:NRC Research Press    

年代:1971

数据来源: NRC

摘要:

Methods for processing the electronic spectra of tetragonal chromium(III) complexes are briefly reviewed. New criteria for assigning the spectra of these complexes are introduced and the data processed to yield a series of crystal field and molecular orbital parameters. The validity of these are discussed with particular reference to the apparent Π bond contribution in the chromium ligand bonds. It is concluded that the bonding is better described in ionic rather than covalent terms.

ISSN:0008-4042    

DOI:10.1139/v71-033

出版商:NRC Research Press    

年代:1971

数据来源: NRC

摘要:

not available

ISSN:0008-4042    

DOI:10.1139/v71-034

出版商:NRC Research Press    

年代:1971

数据来源: NRC

摘要:

Dimethylgermanium dinitrate has been prepared by the reaction of dimethylgermanium dichloride and nitrogen pentoxide in carbon tetrachloride. The properties of this compound have been investigated and compared with those of other known Group IVA alkyl nitrates. The vibrational spectra show that the nitrato groups are covalently bound to the germanium in a unidentate manner. Ultraviolet spectra and conductivity measurements indicate that the compound behaves as a 1:2 electrolyte in water and dimethyl sulfoxide but is a non-electrolyte in methyl cyanide, nitromethane, and ethyl acetate. The complexes Me2Ge(NO3)2•py and Me2Ge(NO3)2•2,2′dipy have been prepared and the infrared spectra of these compounds indicate considerable weakening of the germanium-nitrato bonds.

ISSN:0008-4042    

DOI:10.1139/v71-035

出版商:NRC Research Press    

年代:1971

数据来源: NRC

摘要:

The formation of [(H2O)(NH3)4Ru—N2—Os(NH3)5]4+by the reaction ofcis-Ru(NH3)4(H2O)22+and Os(NH3)5N22+has been studied over the range 15–45 °C. The reaction followed second order kinetics withkt = 1.2 × 10–1 M–1 s–1at 25.0 °C andEa = 16.8 ± 0.1 kcal/mole. Measurement of equilibrium concentrations gaveKeq = 4 × 103 M−1at 25.0 °C.The (4+) dimer was stable but removal of the excesscis-Ru(NH3)4(H2O)22+reactant by oxidation at −0.10 V was followed by dimer decomposition. The breakup obeyed simple first order kinetics withkr = 2.9 × 10−5 s−1at 25.0 °C.Oxidation of the (4+) dimer at + 0.10 V gave a stable (5+) dimer. Removal of the excess Os(NH3)5N22+reactant at + 0.30 V was followed by decomposition of the (5+) dimer giving Os(NH3)5N22+and RuIII(NH3)4X2. The decomposition again obeyed first order kinetics withk1 = 1.5 × 10−5 s−1at 25.0 °C. The (5+) dimer has an intervalence–transfer absorption band at 755 nm and is characterized as [X(NH3)4RuIII—N2—OsII(NH3)5]5+.The studies were carried out in an aqueous H2SO4–K2SO4electrolyte of pH3.3, µ = 0.30.

ISSN:0008-4042    

DOI:10.1139/v71-036

出版商:NRC Research Press    

年代:1971

数据来源: NRC

摘要:

The effects of Co(acetylacetonate)2, Ni(acetylacetonate)2, and Cu(ethyl acetoacetate)2on the nuclear magnetic resonance spectra of a variety of alcohols and amines have been studied. Changes are produced in the spectra, which are useful for assigning the signals.

ISSN:0008-4042    

DOI:10.1139/v71-037

出版商:NRC Research Press    

年代:1971

数据来源: NRC

摘要:

The heats of solution of sodium chlorate in water, and in several water-dioxane mixtures, have been determined experimentally at concentrations of salt ranging from 0.01 molal to saturation. For the dilute region, a direct method was used but for the concentrated range the method was that of diluting the saturated solution. The free energy decreases due to dilution have been calculated from previously determined activity coefficients. Using these data, the entropy changes have been evaluated.The graph of heat of solutionvs. concentration of sodium chlorate passes through a minimum for the solutions more concentrated in dioxane, but not for water and weak dioxane mixtures. A tentative explanation of this is offered.

ISSN:0008-4042    

DOI:10.1139/v71-038

出版商:NRC Research Press    

年代:1971

数据来源: NRC