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1
F– + CF3Br
F–(CF3Br)
[FCF3Br]–
(CF4)Br–
CF4 + Br–
2
F– + CF3Br
F–(BrCF3)
CF4 + Br–
(CF4)Br–
[FCF3Br]–TS TS
ComplexF–(CF3Br)
3
F– + CF3Br
F–(CF3Br)
[FCF3Br]–
(CF4)Br–
CF4 + Br–
(FBrCF3)–
TSTS
Complex
4
5
Table 1.
Enthalpy (kcal/mol) Entry Description B3LYP//B3LYP a MPW1PW91//B3LYP b Experimental
F– + CF3Br Reactants 0.0 0.0 F–(BrCF3) Front-side attack entrance complex –31.0 –30.6 [FBrCF3]– Rotation transition state 1 –7.3 –7.1
F–(BrF2CF) Rotation complex –8.4 –8.3 [FF2CFBr]– Rotation transition state 2 –4.8 –4.6 F–(CF3Br) Back-side attack complex –8.2 –8.1 [FCF3Br]– Back-side attack transition state –7.0 –6.6 Br–(CF4) Back-side attack exit complex –61.4 –63.9 Br– + CF4 Products –59.9 –62.2 –59.4
a B3LYP/6-311+G(3df)//B3LYP/6-311+G(d) b MPW1PW91/6-311+G(3df)//B3LYP/6-311+G(d)
Computational Results
Table 2.
Enthalpy (kcal/mol) Entry Description B3LYP//B3LYP a MPW1PW91//B3LYP b Experimental
F– + CF3I Reactants 0.0 0.0 F–(ICF3) Front-side attack entrance complex –45.2 –45.7 [FICF3]– Rotation transition state 1 –8.8 –8.8
F–(IF2CF) Rotation complex –11.3 –11.8 [FF2CFI]– Rotation transition state 2 –4.8 –4.8 F–(CF3I) Back-side attack complex –8.1 –8.8 [FCF3I]– Back-side attack “transition state” –8.3 –9.1 I–(CF4) Back-side attack exit complex –70.7 –75.3 I– + CF4 Products –69.6 –74.0 –67.9
a B3LYP/[6-311+G(3df):LANL2DZdp ECP dp]//B3LYP/[6-311+G(d):LANL2DZdp ECP] b MPW1PW91//[6-311+G(3df):LANL2DZdp ECP dp]//B3LYP/[6-311+G(d):LANL2DZdp ECP]
6
722
Finding Analytical Functions
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[CF3ClBr]–
Cl– + CF3Br
ClCF3 + Br–
Cl–(BrCF3) (CF3Cl)Br–
9
10
Cl– + CF3Br
ClCF3 + Br–
Cl–(CF3Br)
(ClCF3)Br–
[ClCF3Br]–
11
12
Cl– + CF3Br
ClCF3 + Br–
[ClCF3Br]–
Cl–(BrCF3)(CF3Cl)Br–
Cl–(CF3Br)
(ClCF3)Br–