Litcius/Paper detail

The Grignard Reaction – Unraveling a Chemical Puzzle

Raphael Mathias Peltzer, Jürgen Gauß, Odile Eisenstein, Michele Cascella

2020Journal of the American Chemical Society154 citationsDOIOpen Access PDF

Abstract

bond, cannot occur unless a substrate with a low-lying π*(CO) orbital coordinates the Mg center. This rationalizes why a radical mechanism is detected only in the presence of substrates with a low reduction potential. This feature, in turn, does not necessarily favor the nucleophilic addition, as shown for the reaction with fluorenone. The solvent needs to be considered as a reactant for both the nucleophilic and the radical reactions, and its dynamics is essential for representing the energy profile. The similar reactivity of several species in fast equilibrium implies that the reaction does not occur via a single process but by an ensemble of parallel reactions.

Topics & Concepts

ChemistryNucleophileHomolysisFluorenoneBond cleavagePhotochemistryReactivity (psychology)Reaction mechanismComputational chemistryRadicalOrganic chemistryCatalysisAlternative medicineMedicinePolymerFluorenePathologyCoordination Chemistry and OrganometallicsAsymmetric Synthesis and CatalysisChemical Reaction Mechanisms
The Grignard Reaction – Unraveling a Chemical Puzzle | Litcius