Geometrically enforced donor-facilitated dehydrocoupling leading to an isolable arsanylidine-phosphorane

A proximate Lewis basic group facilitates the mild dehydrogenative P–As intramolecular coupling in the phosphine-arsine peri-substituted acenaphthene 3 , affording thermally and hydrolytically stable arsanylidine-phosphorane 4 with a sterically accessible two-coordinate arsenic atom. The formation of 4 is thermoneutral due to the dehydrogenation being concerted with the donor coordination. Reaction of 4 with a limited amount of oxygen reveals arsinidene-like reactivity via formation of cyclooligoarsines, supporting the formulation of the bonding in 4 as base-stabilized arsinidene R3P→AsR.

Citation

Chalmers , B A , Buehl , M , Athukorala Arachchige , K S , Slawin , A M Z & Kilian , P 2014 , ' Geometrically enforced donor-facilitated dehydrocoupling leading to an isolable arsanylidine-phosphorane ' , Journal of the American Chemical Society , vol. 136 , no. 17 , pp. 6247-6250 . https://doi.org/10.1021/ja502625z

Publication

Journal of the American Chemical Society

Status

Peer reviewed

DOI

https://doi.org/10.1021/ja502625z

ISSN

0002-7863

Type

Journal article

Rights

Copyright © 2014 American Chemical Society. This is an open access article available under the terms of the of the Creative Commons Attribution 4.0 International license. Any use of the article is subject to the following conditions: The authors' moral right to the integrity of their work under the Berne Convention (Article 6bis) is not compromised & where content in the article is identified as belonging to a third party, it is your responsibility to ensure that any reuse complies with copyright policies of the owner.

Description

This work was made open access through funds from the RCUK open access block grant.

Collections

University of St Andrews Research

URI

http://hdl.handle.net/10023/4822