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 Eph 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

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