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1H and 13C NMR studies on 1,3,2-dioxarsolanes

✍ Scribed by D. W. Aksnes; A. Lie

Publisher
John Wiley and Sons
Year
1983
Tongue
English
Weight
760 KB
Volume
21
Category
Article
ISSN
0749-1581

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✦ Synopsis

The 'H and -C NMR spectra of a series of 1,3,2-dioxarsolanes have been obtained at 2.1T and some at 9.4T. The chemical shifts and spin-spii coupling constants have been obtained from complete spectral analyw of the 'H and proton-coupled -C spectra. The spectral data are interpreted on the basis of two rapidly interconverting half-chair conformers with a pseudoaxial substituent at arsenic. Unique assignment of syn/anti or cis/trans geometries have been made from 'H or =C NMR spectroscopy alone. The syn and trans isomers of the 4-methyl-and 4,5-dhnethyl-1,3,2-dioxarsolanes, respectively, appear to be conformationally biased towards the forms with pseudoequatorial methyl groups. The general trends in the geminal and vieinal 'H-lH and =C-'H coupling constants are interpreted in terms of stereospecific, eledronegativity and lone-pair effects of the oxygen heteroatoms and conformational factors. The N M R data on the 1,3,2dioxarsolanes are discussed with reference to related 1,3-dioxa-and 1,3-dithia-five-membered rings with As, P, S or C at the 2-position.

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