ISSN:
0030-4921
Schlagwort(e):
Chemistry
;
Analytical Chemistry and Spectroscopy
Quelle:
Wiley InterScience Backfile Collection 1832-2000
Thema:
Chemie und Pharmazie
Notizen:
The energy difference (ΔE) between the two types of rotamers of β-methoxyethylmercuric chloride has been satisfactorily determined by only assuming the ratio of vicinal trans and gauche H—H coupling constants. The validity of the result was confirmed by the large temperature dependence of the vicinal Hg—H couplings in various solvents. Moreover, it has become possible to determine small values of ΔE in nonpolar solvents. Two ΔE values of β-methoxypropylmercuric chloride in various solvents were determined on the basis of the substituent electronegativity effect on the H—H couplings and their validity was supported by the large temperature dependence of the vicinal Hg—H couplings. With regard to erythro- and threo-(α-methyl-β-methoxy)propylmercuric chlorides, both the H—H and Hg—H couplings were used to estimate the values of ΔE among the rotamers. Throughout the mercury compounds, it was ascertained that the more polar the solvent, the greater the preference for the conformation with the trans disposed HgCl and OCH3 groups. Excellent agreement between the observed facts and the calculations by extended Hückel theory were shown with regard to the relative magnitude of the rotamer polarity and the conformational energy difference of these mercury compounds.
Zusätzliches Material:
3 Ill.
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1002/mrc.1270060808
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