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

Autor:	Santhanathan S. Kumaravel, Setharampattu S. Krishnamurthy, Jayaraman Chandrasekhar, Ramaswamy Murugavel, Munirathinam Nethaji
Rok vydání:	1994
Předmět:	Bond length chemistry.chemical_compound chemistry Organic base Ab initio quantum chemistry methods Stereochemistry Molecule Protonation General Chemistry Crystal structure Guanidine Lone pair
Zdroj:	Journal of the Chemical Society, Dalton Transactions. :847
ISSN:	1364-5447 0300-9246
DOI:	10.1039/dt9940000847
Popis:	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.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::1d4512c4eb861bc9f20d9e4f03b7cef9 https://doi.org/10.1039/dt9940000847 Zobrazit plný text záznamu