The Oxidative Mechanism in Electrophilic CH Activation: The Case of CH₂F₂ and CH₂Cl₂

Abstract

The H(.)-atom transfer (HAT) reaction is investigated in the gas phase, starting from two different entrance channels, O(2)(.+)/CH(2)X(2) and CH(2)X(2)(.+)/O(2) (X=F, Cl), that correspond to a step of hydride transfer and to HAT, respectively. Analysis of the spin and charge along the reaction pathway shows that HAT occurs through the same reacting configuration, irrespective of whether the reactants are formed within the complex or are free isolated species.

Transformation of Chlorohydrocarbons and Amines in the Coordination Sphere of [(µ‐H)2Os3(CO)10]

“…When bromine or iodine was used in place of chlorine in the halohydrocarbons, [(μ-H)Os 3 (μ-X)(CO) 10 ] (X = Br, I) clusters were obtained in good yields, which apparently indicates the replacement of the S N 2 mechanism by S N 2Hal. located on the metal atom are generally used to build or expand metal polyhedra, [29][30][31][32][33][34] that is, nucleophilic attack is aimed at the metal atom of another complex. Several examples of polymetallic carbonyl anion reactions with electrophiles are known to have led to the formation of a metal-electrophile bond.…”

“…The products of their reactions with electrophiles mostly contain a C–X (X = S, Se, Te) bond. Metallate anions with charge mainly located on the metal atom are generally used to build or expand metal polyhedra, that is, nucleophilic attack is aimed at the metal atom of another complex. Several examples of polymetallic carbonyl anion reactions with electrophiles are known to have led to the formation of a metal–electrophile bond.…”