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)

Abstract

One of us recently reported [1] the ³¹P NMR spectrum of neat dichlorophosphinylphosphorimidic trichloride (I) at ca 40 °C. Under these conditions the P_α and P_β 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