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Updated: May 15, 2025

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Intramolecular Electron Exchange Induced Oxygenation of Aldimine Functions of
Mitrali Biswas1, Sanchaita Dey1, Sanjib Panda1,2
1Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, 400076, India.
Abstract:
The article describes stepwise oxygenation of the aldimine functions at the backbone of N,N'-bis(pyridin-2-ylmethylene)naphthyl-1,5-diimine (L) in noninterconvertible L-bridged isomeric diruthenium(II)-acac complexes [{RuII(acac)2}2(μ-L)] (cis-1a/trans-1b, acac = acetylacetonate, DFT calculated ΔEcis-trans = 440 cm-1) via dioxygen activation. It leads to the formation of the corresponding carboxamido bridged [{RuIII(acac)2}2(μ-Ld 2-)] (cis-1ad/trans-1bd; d denotes doubly-oxygenation) with the concomitant metal oxidation. However, L in doubly oxidized (RuIIIRuIII) congeners, i.e., [{RuIII(acac)2}2(μ-L)](ClO4)2 (cis-[1a](ClO4)2/trans-[1b](ClO4)2) as well as electron-poor metal fragments derived [{RuII(bpy)2}2(μ-L)]4+ [2](ClO4)4 (bpy = 2,2'-bipyridine) and [{RuII(PPh3)2(CO) (H)}2(μ-L)]2+ [3](ClO4)2 failed to undergo the aforestated oxygenation process on purging O2 even at elevated temperature due to the absence of necessary electron exchange between ruthenium and L (i.e., RuII-L-RuII↔RuIII-L•--RuII) to initiate the oxygen activation step. Besides structural and spectroscopic characterization of the complexes, oxygenation processes were further monitored through electrochemical, EPR and kinetic experiments in conjunction with DFT calculations, which highlighted mechanistic insights into the reaction sequence.
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