Related Experiment Video
Updated: Dec 6, 2025
Preparation of Polyoxometalate-based Photo-responsive Membranes for the Photo-activation of Manganese Oxide Catalysts
Published on: August 7, 2018
A facile biomimetic catalytic activity through hydrogen atom abstraction by the secondary coordination sphere in
Narayan Ch Jana1, Paula Brandão2, Antonio Frontera3
1Department of Chemistry, Panskura Banamali College, Panskura RS, WB 721152, India. ampanja@yahoo.co.in.
Abstract:
This paper describes the synthesis and structural characterization of four new manganese(iii) complexes (1-4) derived from N3O donor Schiff base ligands and their biomimetic catalytic activities related to catechol oxidase and phenoxazinone synthase. X-ray crystallography reveals that the Schiff bases coordinate the metal centre in a tridentate fashion, leaving the pendant tertiary amine nitrogen atom either protonated or free to balance the charge of the system, and these pendant triamines participate in strong hydrogen bonding interactions in the solid state. The hydrogen bonding ability of the pendant triamines at the second coordination sphere plays a crucial role in the substrate recognition and the stability of the complex-substrate intermediates. The effect of substitution at the phenolate ring towards the redox potential of the metal centre and the catalytic activity of these complexes has been observed. Detailed kinetic studies further disclose the deuterium kinetic isotope effect in which the transfer of the proton along the hydrogen bond from the substrates to the pendant triamine group at the secondary coordination sphere occurs at the key step in the catalytic reaction. The present reactivity nicely resembles the biochemical reactivities in the natural system in which a concerted electron and proton transfer to different species is usually observed. Remarkably, although some sort of influence of the secondary coordination sphere on catalytic activity has been reported mimicking the function of these metalloenzymes, such a direct participation of the secondary coordination sphere, particularly in modelling phenoxazinone synthase, has not been observed to date.
Related Concept Videos
01:21Radical Oxidation of Allylic and Benzylic Alcohols
02:42Valence Bond Theory
02:17Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
02:51Metal-Ligand Bonds
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
02:34Structural Isomerism
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can...
03:02Colors and Magnetism
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...