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Issue 40, 2014
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Phosphinimine-substituted boranes and borenium ions

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The phosphinimines R3PNSiMe3 (R = t-Bu: 1a, R = Cy: 1b, R = Et: 1c, R = Ph: 1d) are reacted with a series of chloro and fluoroboranes (9Cl-9-BBN, (C6F5)2BCl, PhBCl2 and Mes2BF) to access a family of phosphinimine-substituted boranes (2a–d, 3b–d, 4c,d and 6a,b) via Me3SiX elimination (X = Cl, F). The steric and electronic factors governing the formation of monomeric or dimeric products (7c,d) are presented. In addition, in some cases a Lewis acid mediated exchange of Si-bonded methyl groups for a chloro-substituent was observed (5a,b). Based on the phosphinimine-substituted boranes, a series of borenium ion salts (8b–d, 9c, 10b–d) was prepared upon reaction with MeOTf. All compounds were fully characterized and a number of molecular structures were determined by X-ray diffraction.

Graphical abstract: Phosphinimine-substituted boranes and borenium ions

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Article information

07 Aug 2014
25 Aug 2014
First published
26 Aug 2014

Dalton Trans., 2014,43, 15201-15211
Article type

Phosphinimine-substituted boranes and borenium ions

M. H. Holthausen, I. Mallov and D. W. Stephan, Dalton Trans., 2014, 43, 15201
DOI: 10.1039/C4DT02406K

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