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Issue 5, 2012
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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

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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.

Graphical abstract: 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

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Publication details

The article was received on 11 Dec 2011, accepted on 14 Jan 2012 and first published on 23 Feb 2012


Article type: Edge Article
DOI: 10.1039/C2SC01050J
Citation: Chem. Sci., 2012,3, 1656-1661

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    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

    S. E. Bajwa, T. E. Storr, L. E. Hatcher, T. J. Williams, C. G. Baumann, A. C. Whitwood, D. R. Allan, S. J. Teat, P. R. Raithby and I. J. S. Fairlamb, Chem. Sci., 2012, 3, 1656
    DOI: 10.1039/C2SC01050J

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