The fluorine plus (F+) detachment energy (FPDE) values of (XCN)(3)F+ (X = H, F, Cl) and C5X5NF+ (X = H, F, Cl): a theoretical study

The fluorine plus (F+) detachment energy values (FPDE values) of the oxidat ive fluorinators C3N3X3F+ (X = H, F, Cl), which are structurally based on t he 1,3,5-trihalogenotriazine moiety, and C5NX5F+ (X = H, F. Cl). based on p yridine or pentahalogeno pyridine, have been computed quantum-chemically at the density functional B3LYP hybrid level of theory at a 6-31G(d,p) basis. The gas-phase fluorine plus detachment energy values (FPDE) have been addi tively calibrated by an experimental value for KrF+ and have been determine d to be: DeltaH(FPDE) [(FCN)(3)F+] = 212 kcal mol(-1). DeltaH(FPDE) [(ClCN) (3)F+] = 227 kcal mol(-1): DeltaH(FPDE) [(HCN)(3)F+] = 240 kcal mol(-1); De ltaH(FPDE) [C5H5NF+] = 266 kcal mol(-1); DeltaH(FPDE) [C5F5NF+] = 219 kcal mol(-1) and DeltaH(FPDE) [C5Cl5NF+] = 227 kcal mol(-1). (C) 1001 Elsevier S cience B.V. All rights reserved.