Issue 26, 2024

Hydroxopalladium(iv) complexes prepared using oxygen or hydrogen peroxide as oxidants

Abstract

The cycloneophylpalladium(II) complexes [Pd(CH2CMe2C6H4)(κ2-N,N′-L)], 1 or 2, with L = RO(CH2)3N(CH2-2-C5H4N)2, with R = H or Me, respectively, react with either dioxygen or hydrogen peroxide in the presence of NH4[PF6] to give rare examples of the corresponding hydroxopalladium(IV) complexes [Pd(OH)(CH2CMe2C6H4)(κ3-N,N,N′′-L)][PF6], 3 or 4. The complexes 3 and 4 are stable at room temperature and have been structurally characterized. On heating a solution of 3 or 4 in moist dimethylsulphoxide, selective reductive elimination with C(sp2)–O bond formation is observed, followed by hydrolysis, to give the corresponding pincer complex [Pd(OH)(κ3-N,N,N′′-L)][PF6] and 2-t-butylphenol as major products. A more complex reaction occurs in chloroform solution. The mechanisms of reaction are discussed, supported by DFT calculations.

Graphical abstract: Hydroxopalladium(iv) complexes prepared using oxygen or hydrogen peroxide as oxidants

Supplementary files

Article information

Article type
Paper
Submitted
23 abr. 2024
Accepted
12 jun. 2024
First published
13 jun. 2024

Dalton Trans., 2024,53, 10901-10911

Hydroxopalladium(IV) complexes prepared using oxygen or hydrogen peroxide as oxidants

A. Behnia, M. A. Fard, J. M. Blacquiere and R. J. Puddephatt, Dalton Trans., 2024, 53, 10901 DOI: 10.1039/D4DT01202J

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements