Premium
Borane‐Stabilized Isomeric Dimers of the Phosphaethynolate Anion
Author(s) -
Szkop Kevin M.,
Jupp Andrew R.,
Suter Riccardo,
Grützmacher Hansjörg,
Stephan Douglas W.
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201708646
Subject(s) - boranes , steric effects , chemistry , borane , dimer , dissociation (chemistry) , frustrated lewis pair , medicinal chemistry , ion , bond dissociation energy , stereochemistry , lewis acids and bases , crystallography , organic chemistry , catalysis , boron
The reactions of the phosphaethynolate anion ([PCO] − ) with a range of boranes were explored. BPh 3 and [PCO] − form a dimeric anion featuring P−B bonds and is prone to dissociation at room temperature. The more Lewis acidic borane B(C 6 F 5 ) 3 yields a less symmetric dimer of [PCO] − with P−B and P−O bonds. Less sterically demanding HB(C 6 F 5 ) 2 and H 2 B(C 6 F 5 ) boranes form a third isomer with [PCO] − featuring both boranes bound to the same phosphorus atom. Despite the unexpected thermodynamic preference for P‐coordination, computational data illustrate that electronic and steric features impact the binding modes of the resulting dianionic dimers.