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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

By S E Bajwa, T E Storr, Lauren E Hatcher, T J Williams, C G Baumann, A C Whitwood, D R Allan, S J Teat, Paul R Raithby and I J S Fairlamb

Abstract

Pd 3(OAc) 5NO 2, an impurity in "Pd(OAc) 2" {formally Pd 3(OAc) 6}, emerges as a serious issue in the synthesis of pure Pd II 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 CH 3CN by metallic Pd and air, leading to cyclo(ortho)palladated complexes containing nitrite anion, e.g. Pd(NO 2)(C∧N)L (C∧N = papaverine; L = CH 3CN or DMSO) can be explained by Pd 3(OAc) 5NO 2 acting as the nitrite source. Finally, photocrystallographic metastable linkage isomerisation and complete conversion to an oxygen-bound nitrito complex Pd(η 1-ONO)(C∧N)PPh 3 has been observed

Year: 2012
DOI identifier: 10.1039/c2sc01050j
OAI identifier: oai:opus.bath.ac.uk:29612

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