1,2-Phosphaborines: Hybrid Inorganic/Organic P-B Analogues of Benzene

Photolysis of the cyclic phosphine oligomer [PPh]5 in the presence of pentaarylboroles leads to the formation of 1,2‐phosphaborines by the formal insertion of a phenylphosphinidene fragment into the endocyclic CB bond. The solid‐state structure features a virtually planar central ring with bond len...

Full description

Saved in:
Bibliographic Details
Published in:Angewandte Chemie International Edition 2015-10, Vol.54 (41), p.12083-12086
Main Authors: Barnard, Jonathan H., Brown, Paul A., Shuford, Kevin L., Martin, Caleb D.
Format: Article
Language:English
Subjects:
aromaticity
Benzene
Bonding
boroles
boron
Insertion
Mathematical analysis
Oligomers
Phosphines
phosphorus
Photolysis
Ring currents
ring expansion
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:Photolysis of the cyclic phosphine oligomer [PPh]5 in the presence of pentaarylboroles leads to the formation of 1,2‐phosphaborines by the formal insertion of a phenylphosphinidene fragment into the endocyclic CB bond. The solid‐state structure features a virtually planar central ring with bond lengths indicating significant delocalization. Appreciable ring current in the 1,2‐phosphaborine core, detected in nuclear independent chemical shift (NICS) calculations, are consistent with aromatic character. These products are the first reported 1,2‐BPC4 conjugated heterocycles and open a new avenue for BP as a valence isoelectronic substitute for CC in arene systems. Jamming PB into benzene: 1,2‐Phosphaborines were synthesized by the ring expansion reaction of boroles with the cyclic phosphine [PPh]5 under UV irradiation. The products were structurally characterized revealing a planar central ring. The nature of the bonding was analyzed computationally and indicated that the heterocycle had appreciable aromatic character.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201507003