Selective Oxygen Atom Insertion into an Aryl-Palladium Bond

Authors

Ava Behnia, The University of Western Ontario
Paul D. Boyle, The University of Western Ontario
Johanna M. Blacquiere, The University of Western OntarioFollow
Richard J. Puddephatt, The University of Western Ontario

Document Type

Article

Publication Date

8-22-2016

Journal

Organometallics

Volume

35

Issue

16

First Page

2645

Last Page

2654

URL with Digital Object Identifier

10.1021/acs.organomet.6b00387

Abstract

The chemistry of a palladium(II) complex containing both an alkyl- and an aryl-palladium bond is reported. The reaction of [Pd(CH2CMe2C6H4)(MesN=CHCH=NMes)] with bromine or iodine leads to reductive elimination of 1,1-dimethylcyclobutabenzene with formation of [PdX2(MesN=CHCH=NMes)] (X = Br, I). However, the reaction with hydrogen peroxide gives [Pd(CH2CMe2C6H4O)(MesN=CHCH=NMes)] by overall oxygen atom insertion into the aryl-palladium rather than the alkyl-palladium bond. This complex [Pd(CH2CMe2C6H4O)(MesN=CHCH=NMes)] reacts with bromine, iodine, or hydrogen peroxide to give 3,3-dimethyl-2,3-dihydrobenzofuran and the corresponding complex [PdX2(MesN=CHCH=NMes)]. The mechanisms of reaction and basis for selectivity are discussed. The results support the view that oxygen atom insertion is a mechanistically viable pathway for selective catalytic oxidation of hydrocarbons by the green oxidant hydrogen peroxide.

Citation of this paper:

Ava Behnia, Paul D. Boyle, Johanna M. Blacquiere, and Richard J. Puddephatt Organometallics 2016 35(16), 2645-2654

DOI: 10.1021/acs.organomet.6b00387