Issue 2, 2014

The frustrated Lewis pair pathway to methylene phosphonium systems

Abstract

Reaction of HB(C6F5)2 with (tBu3C6H2)P(vinyl)2 does not yield the expected ethylene-bridged frustrated Lewis pair (FLP) but its cyclic methylene phosphonium isomer which is formed in a unique way by subsequent internal 1,2-P/B addition to the vinylphosphane unit. The product is a rare example of a stable phosphorus analogue of the ubiquitous iminium salts. It features a short P[double bond, length as m-dash]C bond (1.637(3) Å). Subsequent reactions with pyridine and with dihydrogen probably proceed by equilibration with the “invisible” ethylene-bridged FLP isomer. The reaction of (tBu3C6H2)P(vinyl)2 with B(C6F5)3 gave the zwitterionic acyclic methylene phosphonium product that was crystallized at low temperature and isolated. The X-ray crystal structure analysis also revealed a short P[double bond, length as m-dash]C bond (1.635(5) Å).

Graphical abstract: The frustrated Lewis pair pathway to methylene phosphonium systems

Supplementary files

Article information

Article type
Edge Article
Submitted
20 Aug 2013
Accepted
24 Oct 2013
First published
06 Dec 2013

Chem. Sci., 2014,5, 797-803

The frustrated Lewis pair pathway to methylene phosphonium systems

Y. Hasegawa, G. Kehr, S. Ehrlich, S. Grimme, C. G. Daniliuc and G. Erker, Chem. Sci., 2014, 5, 797 DOI: 10.1039/C3SC52327F

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