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

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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

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Publication details

The article was received on 31 Oct 2017, accepted on 30 Jan 2018 and first published on 31 Jan 2018


Article type: Edge Article
DOI: 10.1039/C7SC04687A
Citation: Chem. Sci., 2018, Advance Article
  • Open access: Creative Commons BY license
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    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, Advance Article , DOI: 10.1039/C7SC04687A

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