Issue 31, 2019

Storing redox equivalent in the phenalenyl backbone towards catalytic multi-electron reduction

Abstract

Storing and transferring electrons for multi-electron reduction processes are considered to be the key steps in various important chemical and biological transformations. In this work, we accomplished multi-electron reduction of a carboxylic acid via a hydrosilylation pathway where a redox-active phenalenyl backbone in Co(PLY-O,O)2(THF)2, stores electrons and plays a preponderant role in the entire process. This reduction proceeds by single electron transfer (SET) from the mono-reduced ligand backbone leading to the cleavage of the Si–H bond. Several important intermediates along the catalytic reduction reaction have been isolated and well characterized to prove that the redox equivalent is stored in the form of a C–H bond in the PLY backbone via a ligand dearomatization process. The ligand's extensive participation in storing a hydride equivalent has been conclusively elucidated via a deuterium labelling experiment. This is a rare example where the ligand orchestrates the multielectron reduction process leaving only the metal to maintain the conformational requirements and fine tunes the electronics of the catalyst.

Graphical abstract: Storing redox equivalent in the phenalenyl backbone towards catalytic multi-electron reduction

Supplementary files

Article information

Article type
Edge Article
Submitted
25 apr 2019
Accepted
07 jun 2019
First published
10 jun 2019
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2019,10, 7433-7441

Storing redox equivalent in the phenalenyl backbone towards catalytic multi-electron reduction

M. Bhunia, S. R. Sahoo, B. K. Shaw, S. Vaidya, A. Pariyar, G. Vijaykumar, D. Adhikari and S. K. Mandal, Chem. Sci., 2019, 10, 7433 DOI: 10.1039/C9SC02057H

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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