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Formation of the spirocyclic, Si-centered cage cations [ClP(NSiMe3)2Si(NSiMe3)2P5]+ and [P5(NSiMe3)2Si(NSiMe3)2P5]2+

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Abstract

On account of our interest in P4 activation by phosphenium ion insertion into P–P bonds we have developed synthetic routes to bicyclic N–P–Si-heterocycle 7 and probed its reactivity towards GaCl3 and P4. A GaCl3-induced rearrangement of 7 leads to the in situ formation of spirocyclic, Si-centered phosphenium ions. Their insertion into P–P bonds of one or two P4 tetrahedra yields polyphosphorus cages [ClP(NSiMe3)2Si(NSiMe3)2P5]+ (19+) and [P5(NSiMe3)2Si(NSiMe3)2P5]2+ (132+).

Graphical abstract: Formation of the spirocyclic, Si-centered cage cations [ClP(NSiMe3)2Si(NSiMe3)2P5]+ and [P5(NSiMe3)2Si(NSiMe3)2P5]2+

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Article information


Submitted
21 Apr 2015
Accepted
03 Jun 2015
First published
15 Jun 2015

This article is Open Access

Dalton Trans., 2016,45, 1953-1961
Article type
Paper

Formation of the spirocyclic, Si-centered cage cations [ClP(NSiMe3)2Si(NSiMe3)2P5]+ and [P5(NSiMe3)2Si(NSiMe3)2P5]2+

M. H. Holthausen and J. J. Weigand, Dalton Trans., 2016, 45, 1953
DOI: 10.1039/C5DT01512J

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