Mechanism of phosphinidene complex arylation by arylboronic acids
Ng, Yong Xiang
Date of Issue2014
School of Physical and Mathematical Sciences
The arylation reaction of terminal phosphinidene complexes [RP-W(CO)5] by arylboronic acids is very sensitive to steric hindrance and the electronic properties of the substituents on the aryl ring. On the basis of DFT calculations and additional experiments, it seems that the mechanism involves first an insertion of the phosphinidene into one of the B–O bonds, followed by an intramolecular nucleophilic attack of the aryl group onto the P–OH bond promoted by the potassium phosphate. The [1,2]-aryl shift from B to P cannot be reproduced with an alkyl group.
© 2014 American Chemical Society. This is the author created version of a work that has been peer reviewed and accepted for publication by Organometallics, American Chemical Society. It incorporates referee’s comments but changes resulting from the publishing process, such as copyediting, structural formatting, may not be reflected in this document. The published version is available at: [Article DOI: http://dx.doi.org/10.1021/om5001138].