On the rotational isomerism in dichlorophosphinylphosphorimidic trichloride

Glidewell, C., Keat, R. and Rycroft, D. S. (1981) On the rotational isomerism in dichlorophosphinylphosphorimidic trichloride. Inorganica Chimica Acta, 53, L231. (doi:10.1016/S0020-1693(00)84806-9)

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Abstract

One of us recently reported [1] the 31P NMR spectrum of neat dichlorophosphinylphosphorimidic trichloride (I) at ca 40 °C. Under these conditions the Pα and Pβ signals each consisted of three distinct doublets and these were attributed to the presence of three rotamers. The 31P spectrum of (I) in nitrobenzene solution was of the AB-type, J(PNP) = 17.5 Hz, in good agreement with previous results (e.g. ref. 2). However, other work (see ref. 3 for a summary) has shown that in general rotational barriers about P—N bonds involving four co-ordinated phosphorus are such that the effects of restricted rotation are not apparent at ambient temperatures unless the nitrogen and phosphorus atoms have relatively bulky substituents. In the light of the latter findings, we have reinvestigated the 31P NMR of neat samples of (I) at 24.3 and 40.5 MHz, and in all cases only one AB spectrum was obtained.

Item Type:Articles
Keywords:Phosphorus chemistry, NMR spectroscopy.
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Rycroft, Dr David
Authors: Glidewell, C., Keat, R., and Rycroft, D. S.
Subjects:Q Science > QD Chemistry
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Inorganica Chimica Acta
Publisher:Elsevier
ISSN:0020-1693
ISSN (Online):1873-3255

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