10/2013

The Borovik group, in collaboration with the Shaik group, report their findings on the impact of the basicity of a given iron-complex on the reaction pathway in C–H, N–H and O–H bond activation systems.

Through a combination of experimental observations and theoretical findings a comparative picture is constructed of a mechanistic spectrum ranging from concerted hydrogen atom transfer (HAT) and proton-coupled electron-transfer (PCET) mechanisms, through asynchronous proton-transfer (PT)/electron transfer (ET), all the way to PT.

Using a valence bond model the observed results are linked directly to the basicity/acidity of the reagents, but also highlight significant differences in the fundamental pathways of C–H versus N–H and O–H bond functionalization.