On the appearance of nitrite anion in [PdX(OAc)L2] and [Pd(X)(C^N)L] syntheses (X = OAc or NO2): photocrystallographic identification of metastable Pd(η1-ONO)(C^N)PPh3

Bajwa, Somia E., Storr, Thomas E., Hatcher, Lauren E., Williams, Thomas J., Baumann, Christoph G., Whitwood, Adrian C., Allan, David R., Teat, Simon J., Raithby, Paul R. and Fairlamb, Ian J. S. (2012) On the appearance of nitrite anion in [PdX(OAc)L2] and [Pd(X)(C^N)L] syntheses (X = OAc or NO2): photocrystallographic identification of metastable Pd(η1-ONO)(C^N)PPh3. Chemical Science, 3 (5). pp. 1656-1661. ISSN 2041-6520

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Abstract

Pd3(OAc)5NO2, an impurity in “Pd(OAc)2” {formally Pd3(OAc)6}, emerges as a serious issue in the synthesis of pure PdII complexes derived from Pd(OAc)2, for example in our C–H activation precatalyst, Pd(OAc)2(pip)2 (pip = piperidine). A previous proposal that nitrite anion can be formed by oxidation of CH3CN by metallic Pd and air, leading to cyclo(ortho)palladated complexes containing nitrite anion, e.g. Pd(NO2)(C^N)L (C^N = papaverine; L = CH3CN or DMSO) can be explained by Pd3(OAc)5NO2 acting as the nitrite source. Finally, photocrystallographic metastable linkage isomerisation and complete conversion to an oxygen-bound nitrito complex Pd(η1-ONO)(C^N)PPh3 has been observed.

Item Type: Article
Faculty \ School: Faculty of Science > School of Chemistry
Related URLs:
Depositing User: Pure Connector
Date Deposited: 13 Jan 2017 00:06
Last Modified: 22 Apr 2020 02:26
URI: https://ueaeprints.uea.ac.uk/id/eprint/62045
DOI: 10.1039/c2sc01050j

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