Hexaalkoxy and hexaaryloxy 1,3,2λ5,4λ5-diazadiphosphetidines

Kumaravel, S. S. ; Krishnamurthy, S. S. ; Day, Roberta O. ; Holmes, Robert R. (1991) Hexaalkoxy and hexaaryloxy 1,3,2λ5,4λ5-diazadiphosphetidines Phosphorus, Sulfur, and Silicon and the Related Elements, 57 (3&4). pp. 163-172. ISSN 1042-6507

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Official URL: http://www.informaworld.com/index/757932010.pdf

Related URL: http://dx.doi.org/10.1080/10426509108038846


The reaction of the hexachlorodiazadiphosphetidine (MeNPCl3)2 with NaOR (R = CH2CF3 or C6H5) yields the hexaalkoxy/aryloxy derivatives [MeNP(OR)3]2. On the other hand, the reaction of the N-phenyl derivative with NaOCH2CF3 affords the monophosphazene PhN=P(OCH2CF3)3. Spectroscopic data for the new compounds are presented. The structure of the trifluoroethoxy derivative [MeNP(OCH2CF3)3]2 has been confirmed by a single crystal X-ray diffraction study. It crystallizes in the triclinic space group P1 with a = 9.024(2) Å, b = 9.255(2) Å, c = 9.944(2) Å, α= 69.68(2)°, β = 60.16(2)°. γ = 78.88(2)°, and Z = 1. The final conventional unweighted residual is 0.044. The transformation of [MeNP(OCH2CF3)3]2 into its monomer at 110°C and its redistribution reaction with [MeNPF3]2 have been investigated by NMR spectroscopy. The formation of dimeric species appears to be favored by electron withdrawing groups at phosphorus promoting delocalization in the P-N-P system.

Item Type:Article
Source:Copyright of this article belongs to Taylor and Francis Ltd.
Keywords:Diazadiphosphetidine; Monophosphazene; Cyclodiphosphazane; Redistribution; Pseudorotation; X-ray Structure
ID Code:17829
Deposited On:16 Nov 2010 12:38
Last Modified:08 Jun 2011 07:02

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