Dioxygen Activation by Redox-Active Bis(aldimine) Ligand Bridged Diruthenium Complex Possessing Singlet Ground State |
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| Authors: | Mitrali Biswas Sanchaita Dey Abhishek Das Prof. Dr. Tapan Kanti Paine Dr. Sanjib Panda Prof. Dr. Goutam Kumar Lahiri |
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| Affiliation: | 1. Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, 400076 India;2. School of Chemical Sciences, Indian Association for the Cultivation of Science, Jadavpur, Kolkata, 700032 India |
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| Abstract: | The unexplored ‘actor’ behavior of redox-active bis(aldimine) congener, p-phenylene-bis(picoline)aldimine (L1), towards dioxygen activation and subsequent functionalization of its backbone was demonstrated on coordination with {Ru(acac)2} (acac= acetylacetonate). Reaction under aerobic condition led to the one-pot generation of dinuclear complexes with unperturbed L1, imino-carboxamido (L2−), and bis(carboxamido) (L32−)-bridged isovalent {RuII(μ-L1)RuII}, 1/ {RuIII(μ-L32−)RuIII}, 3 and mixed-valent {RuII(μ-L2−)RuIII}, 2 . Authentication of the complexes along with the redox non-innocence behavior of their bridge have been validated through structure, spectroelectrochemistry and DFT calculations. Kinetic and isotope labelling experiments together with DFT analyzed transition states justified the consideration of redox shuttling at metal/L1 interface for 3O2 activation despite of the closed shell configuration of 1 (S=0) to give carboxamido derived 2 / 3 . |
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| Keywords: | aldimine dioxygen activation DFT calculations radical reactivity redox non-innocence |
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