Chemistry Publications

Title

Mild and selective Pd-Ar protonolysis and C-H activation promoted by a ligand aryloxide group

Document Type

Article

Publication Date

1-1-2018

Journal

Dalton Transactions

Volume

47

Issue

10

First Page

3538

Last Page

3548

URL with Digital Object Identifier

10.1039/c8dt00437d

Abstract

A bidentate nitrogen-donor ligand with an appended phenol group, C5H4NCHN-2-C6H4OH, H(L1) was treated with a palladium cycloneophyl complex [Pd(CH2CMe2C6H4)(COD)], with both Pd-aryl and Pd-alkyl bonds, to give a Pd-alkyl complex, [Pd(CH2CMe2C6H5)(κ3-N,N′,O-OC6H4NCH(2-C5H4N))], 1. The cleavage of the Pd-aryl bond and the deprotonation of the ligand phenol to afford a bound aryloxide, indicates facile Pd-aryl bond protonolysis. Deuterium labelling experiments confirmed that the ligand phenol promotes protonolysis and that the reverse, aryl C-H activation, occurs under very mild reaction conditions (within 10 min at room temperature). An unusual isomerization of the Pd-alkyl complex 1 to a Pd-aryl complex, [Pd(C6H4(2-t-Bu))(κ3-N,N′,O-OC6H4NCH(2-C5H4N))], 2, was observed to give an equilibrium with [2]/[1] = 9 after 5 days in methanol. The isomerization requires that both aryl C-H activation and Pd-alkyl protonolysis steps occur. The very large KIE value (kH/kD = ca. 40) for isomerization of 1 to 2, suggests a concerted SE2-type mechanism for the Pd-alkyl protonolysis step.

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