Issue 10, 2018

Tuning the redox non-innocence of a phenalenyl ligand toward efficient nickel-assisted catalytic hydrosilylation

Abstract

In this report, a ligand-redox assisted catalytic hydrosilylation has been investigated. A phenalenyl ligand coordinated nickel complex has been utilized as an electron reservoir to develop a base metal-assisted catalyst, which very efficiently hydrosilylates a wide variety of olefin substrates under ambient conditions. A mechanistic investigation revealed that a two-electron reduced phenalenyl based biradical nickel complex plays the key role in such catalysis. The electronic structure of the catalytically active biradical species has been interrogated using EPR spectroscopy, magnetic susceptibility measurements, and electronic structure calculations using a DFT method. Inhibition of the reaction by a radical quencher, as well as the mass spectrometric detection of two intermediates along the catalytic loop, suggest that a single electron transfer from the ligand backbone initiates the catalysis. The strategy of utilising the redox reservoir property of the ligand ensures that the nickel is not promoted to an unfavorable oxidation state, and the fine tuning between the ligand and metal redox orbitals elicits smooth catalysis.

Graphical abstract: Tuning the redox non-innocence of a phenalenyl ligand toward efficient nickel-assisted catalytic hydrosilylation

Supplementary files

Article information

Article type
Edge Article
Submitted
31 Okt. 2017
Accepted
30 Janv. 2018
First published
31 Janv. 2018
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., 2018,9, 2817-2825

Tuning the redox non-innocence of a phenalenyl ligand toward efficient nickel-assisted catalytic hydrosilylation

G. Vijaykumar, A. Pariyar, J. Ahmed, B. K. Shaw, D. Adhikari and S. K. Mandal, Chem. Sci., 2018, 9, 2817 DOI: 10.1039/C7SC04687A

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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