LAUSR

Abstract The mechanism of silver(I)-mediated trifluoromethylation of aryldiazonium salts has been studied comprehensively with density functional theory (DFT). Three stages constitute the trifluoromethylation pathway, namely (i) dissociation of the aryldiazonium salt, (ii) formation of the key disilver(I) intermediate and (iii) disilver(I)-mediated oxidative addition/reductive elimination (OA/RE) reaction. Thereinto, oxidative addition is the rate-determining step in the whole reaction. A radical pathway can be ruled out according to the present calculations. Moreover, the counterion in aryldiazonium salt has great influences on the trifluoromethylation as follows: (i) affecting the dissociation of aryldiazonium salt; (ii) participating in the formation of disilver(I) intermediates.