Issue 40, 2011

Donor-stabilised cations, phosphinamide anions, and unusual oxidative cyclisation products from halogenated phosphoranimines and phosphinimines with a bulky 2,4,6-tri-tert-butylphenyl substituent at nitrogen

Abstract

New aspects of the chemistry of the phosphoranimine Cl3P[double bond, length as m-dash]NMes* (Mes* = 2,4,6-tri-tert-butylphenyl) (7) and the phosphinimine ClP[double bond, length as m-dash]NMes* (2) have been explored. A cationic derivative of 7 was prepared from the reaction between this species and DMAP (DMAP = 4-dimethylaminopyridine) in the presence of the halide abstraction agent AgOTf (OTf = OSO3CF3) which yielded the donor-stabilized cation [DMAP–PCl2[double bond, length as m-dash]NMes*]+ ([9]+). When treated with tertiary phosphinesnBu3P or Ph3P, 7 was found to undergo a reductive dechlorination reaction to yield 2 and dichlorophosphoranes R3PCl2 (R = nBu (13a), Ph (13b)). The phosphinimine 2 reacts with Cl sources to form the novel dichlorophosphinamide anion [Cl2PNMes*] ([14]) which was characterized in solution. Treatment of [Ph4P][14], generated in situ, with GaCl3 or MeOTf regenerated 2 and provided further evidence for the formation of the anion [14]. In addition, phosphoranimine 2 was found to undergo an unexpected oxidative cyclization reaction when treated with the oxygen transfer agent pyridine-N-oxide to yield a P-chlorophosphoryl-ox-3-azoline (18).

Graphical abstract: Donor-stabilised cations, phosphinamide anions, and unusual oxidative cyclisation products from halogenated phosphoranimines and phosphinimines with a bulky 2,4,6-tri-tert-butylphenyl substituent at nitrogen

Supplementary files

Article information

Article type
Paper
Submitted
12 Apr 2011
Accepted
06 May 2011
First published
19 Jul 2011

Dalton Trans., 2011,40, 10576-10584

Donor-stabilised cations, phosphinamide anions, and unusual oxidative cyclisation products from halogenated phosphoranimines and phosphinimines with a bulky 2,4,6-tri-tert-butylphenyl substituent at nitrogen

K. Huynh, C. P. Chun, A. J. Lough and I. Manners, Dalton Trans., 2011, 40, 10576 DOI: 10.1039/C1DT10641D

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements