Reactions of the hexachlorocyclodiphosphazane [MeNPCl3]2 with primary aromatic amines: formation of highly basic bisphosphinimines

Murugavel, Ramaswamy and Kumarave, Santhanathan S and Krishnamurthy, Setharampattu S and Nethaji, Munirathinam and Chandrasekha, Jayaraman (1994) Reactions of the hexachlorocyclodiphosphazane [MeNPCl3]2 with primary aromatic amines: formation of highly basic bisphosphinimines. In: Dalton Transactions (6). 847-852 .

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Abstract

Reactions of hexachlorocyclodiphosphazane [MeNPCl3]2 with primary aromatic amines afforded the bisphosphinimine hydrochlorides [(RNH)2(RN)PN(Me)P(NHMe)(NHR)2]+Cl- (R = Ph 1, C6H4Me-4 2 or C6H4OMe-4 3). Dehydrochlorination of 2 and 3 by methanolic KOH yielded highly basic bisphosphinimines [(RNH)2(RN)PN(Me)P(NMe)(NHR)2] (R = C6H4Me-4 4 or C6H4OMe-4 5). Compounds 1-5 have been characterised by elemental analysis and IR and NMR (H-1, C-13, P-31) spectroscopy. The structure of 2 has been confirmed by single-crystal X-ray diffraction. The short P-N bond lengths and the conformations of the PN, units can be explained on the basis of cumulative negative hyperconjugative interactions between nitrogen lone pairs and adjacent P-N sigma* orbitals. Ab initio calculations on the model phosphinimine (H2N)3P=NH and its protonated form suggest that (amino)phosphinimines would be stronger bases compared to many organic bases such as guanidine.

Item Type:	Journal Article
Publication:	Dalton Transactions
Publisher:	Royal society of chemistry
Additional Information:	Copyright of this article belongs to Royal society of chemistry.
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry Division of Chemical Sciences > Organic Chemistry
Date Deposited:	11 Apr 2011 06:50
Last Modified:	11 Apr 2011 06:50
URI:	http://eprints.iisc.ac.in/id/eprint/36779

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