Related Experiment Video
Updated: Mar 8, 2026

Thermochemical Studies of NiII and ZnII Ternary Complexes Using Ion Mobility-Mass Spectrometry
Published on: June 8, 2022
Sterically directed nitronate complexes of 2,6-di-tert-butyl-4-nitrophenoxide with Cu(ii) and Zn(ii) and their H-atom
Thomas R Porter1, Ellen C Hayes2, Werner Kaminsky2
1Department of Chemistry, University of Washington, Box 351700, Seattle, Washington 98195-1700, USA and Laboratoire d'Electrochimie Moléculaire, Université Paris Diderot, Bâtiment Lavoisier, 15 rue Jean de Bäif, 75205 Paris Cedex 13, France.
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. TptBuCuII(κ2-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.
More Related Videos
10:51The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
19:58Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
Related Concept Videos
meta-Directing Deactivators: –NO2, –CN, –CHO, –⁠CO2R, –COR, –CO2H
1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Mechanism
Diazonium Group Substitution: –OH and –H
ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3
1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Overview
The nitrous acid is unstable. Hence, it is formed in situ from a solution of sodium nitrite and cold aqueous acids such as hydrochloric or sulfuric acid. In an acidic solution, the –OH group of nitrous acid undergoes protonation to give oxonium ion, followed by...
Coordination Number and Geometry