Issue 5, 2012
From the journal:

Chemical Science

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†

Somia E. Bajwa,a   Thomas E. Storr,ab   Lauren E. Hatcher,c   Thomas J. Williams,a   Christoph G. Baumann,b   Adrian C. Whitwood,a   David R. Allan,d   Simon J. Teat,e   Paul R. Raithby*c  and  Ian J. S. Fairlamb*a  

* Corresponding authors

a Department of Chemistry, University of York, York, UK
E-mail: ian.fairlamb@york.ac.uk
Fax: +0044 (0)1904 322516
Tel: +0044 324091

b Department of Biology, University of York, York, UK
Tel: +0044 (0)1904 328828

c Department of Chemistry, University of Bath, Bath, UK
E-mail: p.r.raithby@bath.ac.uk
Fax: +0044 (0)1225 383 183

d Diamond Light Source Ltd, Diamond House, Harwell Science and Innovation Campus, Didcot, Oxfordshire, UK

e Advanced Light Source, Lawrence Berkeley National Laboratory Berkeley, Berkeley, USA

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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Article information

DOI
https://doi.org/10.1039/C2SC01050J
Article type
Edge Article
Submitted
11 Dec 2011
Accepted
14 Jan 2012
First published
23 Feb 2012

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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