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Issue 8, 2017
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Sterically directed nitronate complexes of 2,6-di-tert-butyl-4-nitrophenoxide with Cu(ii) and Zn(ii) and their H-atom transfer reactivity

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Abstract

The bulky 2,6-di-tert-butyl-4-nitrophenolate ligand forms complexes with [TptBuCuII]+ and [TptBuZnII]+ binding via the nitro group in an unusual nitronato-quinone resonance form (TptBu = hydro-tris(3-tert-butyl-pyrazol-1-yl)borate). The Cu complex in the solid state has a five-coordinate κ2-nitronate structure, while the Zn analogue has a four-coordinate κ1-nitronate ligand. 4-Nitrophenol, without the 2,6-di-tert-butyl substituents, instead binds to [TptBuCuII]+ through the phenolate oxygen. This difference in binding is very likely due to the steric difficulty in binding a 2,6-di-tert-butyl-phenolate ligand to the [TptBuMII]+ unit. TptBuCuII2-O2NtBu2C6H2O) reacts with the hydroxylamine TEMPO–H (2,2,6,6-tetramethylpiperidin-1-ol) by abstracting a hydrogen atom. This system thus shows an unusual sterically enforced transition metal–ligand binding motif and a copper–phenolate interaction that differs from what is typically observed in biological and chemical catalysis.

Graphical abstract: Sterically directed nitronate complexes of 2,6-di-tert-butyl-4-nitrophenoxide with Cu(ii) and Zn(ii) and their H-atom transfer reactivity

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Publication details

The article was received on 22 Nov 2016, accepted on 16 Jan 2017 and first published on 17 Jan 2017


Article type: Paper
DOI: 10.1039/C6DT04427A
Dalton Trans., 2017,46, 2551-2558

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    Sterically directed nitronate complexes of 2,6-di-tert-butyl-4-nitrophenoxide with Cu(II) and Zn(II) and their H-atom transfer reactivity

    T. R. Porter, E. C. Hayes, W. Kaminsky and J. M. Mayer, Dalton Trans., 2017, 46, 2551
    DOI: 10.1039/C6DT04427A

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