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A peroxynitrite complex of copper: formation from a copper–nitrosyl complex, transformation to nitrite and exogenous phenol oxidative coupling or nitration

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Abstract

Reaction of nitrogen monoxide with a copper(I) complex possessing a tridentate alkylamine ligand gives a Cu(I)–(·NO) adduct, which when exposed to dioxygen generates a peroxynitrite (O=NOO−)–Cu(II) species. This undergoes thermal transformation to produce a copper(II) nitrito (NO2 –) complex and 0.5 mol equiv O2. In the presence of a substituted phenol, the peroxynitrite complex effects oxidative coupling, whereas addition of chloride ion to dissociate the peroxynitrite moiety instead leads to phenol ortho nitration. Discussions include the structures (including electronic description) of the copper–nitrosyl and copper–peroxynitrite complexes and the formation of the latter, based on density functional theory calculations and accompanying spectroscopic data.

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Notes

  1. A weak 655 nm absorption observed is believed to be from a dimer form with bridging NO ligands, Cu II2 –(NO−)2; further investigations are required.

  2. As a general check of the validity of the calculations and the basis set employed in this report, they were repeated for the nitrito complex with known X-ray structure (described in this paper), [CuII(AN)(NO2 −)]+, using two different (larger) basis sets. First, the calculations used a TZVP basis set for the copper atom. Then, an additional set of diffuse functions was added to nonmetal atoms. Although the three optimized structures are very similar to those obtained using the 6-311G* basis set, the latter provided closer agreement with the observed experimental X-ray structure (with its \( d_{{x^{2} - y^{2} }} \) ground state). For these reasons, it was considered appropriate for use in the calculations and the results presented.

Abbreviations

AN:

3,3′-Iminobis(N,N′-dimethylpropylamine)

DFT:

Density functional theory

2,4-DTBP:

2,4-Di-t-butylphenol

tBu4NCl:

Tetrabutylammonium chloride

THF:

Tetrahydrofuran

TMG3tren:

Tris(2-(N-tetramethylguanidyl)ethyl)amine

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Acknowledgments

We are grateful to the NIH (K.D.K., GM28962; E.I.S., DK31450) for research support. D.R. thanks the Sixth Framework Programme of the EU for an MC-OIF fellowship.

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Authors and Affiliations

  1. Department of Chemistry, Johns Hopkins University, Baltimore, MD, 21218, USA

    Ga Young Park, Subramanian Deepalatha, Simona C. Puiu, Biplab Mondal, Amy A. Narducci Sarjeant & Kenneth D. Karlin

  2. Department of Chemistry, Chonbuk National University, Jeonju, 560-756, Korea

    Dong-Heon Lee

  3. Department of Chemistry, Stanford University, Stanford, CA, 94305, USA

    Diego del Rio, Monita Y. M. Pau & Edward I. Solomon

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  1. Ga Young Park
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  2. Subramanian Deepalatha
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Correspondence to Kenneth D. Karlin.

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G. Y. Park, S. Deepalatha, and S. C. Puiu contributed equally to this work.

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Park, G.Y., Deepalatha, S., Puiu, S.C. et al. A peroxynitrite complex of copper: formation from a copper–nitrosyl complex, transformation to nitrite and exogenous phenol oxidative coupling or nitration. J Biol Inorg Chem 14, 1301–1311 (2009). https://doi.org/10.1007/s00775-009-0575-8

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