Density functional theory methods are today an indispensible tool in the study of reaction mechanisms of homogenous catalysis. Quite large systems can be treated quite accurately and reasonably fast. Accordingly, this methodology has been applied very successfully to a vast number of different reactions.<br/>This talk will focus on mechanisms and origins of selectivity of a number of metal-catalyzed fluorination reactions. These include: 1) Zn-catalyzed fluorination of alkenes, 2) Rh-catalyzed geminal oxyfluorination and oxytrifluoro-methylation of diazocarbonyls, and 3) Rh-catalyzed oxy-aminofluorination of diazoketones. The first two reactions use a hypervalent iodine reagent, while the last reaction uses N-fluorobenzenesulfonimide (NFSI).<br/>For each of these reactions, the detailed mechanism will be examined and all intermediates and transition states will be characterized in order to produce the free energy profile. Similarities and differences in the reactivity will be highlighted.

Theoretical studies of mechanisms and selectivities of metal-catalyzed fluorination reactions

255th National Meeting (2018)

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