Royal Society of Chemistry

Table 1.4

Computational heats of decomposition ΔE and experimental rates of decomposition k_d of RC(O)O–OC(O)R peroxides.

R	ΔE/kJ mol⁻¹a	k_d/s⁻¹×10⁸
CH₃	20.3 (−30.7)	2b^,c
CH₂F	−25.9 (−66.5)
CHF₂	−56.4 (−86.6)
CF₃	−48.7 (−71.9)	100b^,d
CH₂–CH₃	21.7 (−23.9)	3b^,c
CH₂–CH₂F	26.7 (−18.2)
CH₂–CHF₂	26.7 (−14.5)
CH₂–CF₃	9.9 (−30.9)	1b^,e
CHF–CH₃	−17.0 (−52.3)
CHF–CH₂F	−21.1 (−54.6)
CHF–CHF₂	−23.4 (−56.1)
CHF–CF₃	−33.9 (−65.7)
CF₂–CH₃	−40.1 (−65.3)	96000b^,f
CF₂–CH₂F	−36.3 (−61.2)
CF₂–CHF₂	−42.9 (−66.3)
CF₂–CF₃	−49.7 (−72.6)	1160b^,g

R	ΔE/kJ mol⁻¹a	k_d/s⁻¹×10⁸
CH₃	20.3 (−30.7)	2b^,c
CH₂F	−25.9 (−66.5)
CHF₂	−56.4 (−86.6)
CF₃	−48.7 (−71.9)	100b^,d
CH₂–CH₃	21.7 (−23.9)	3b^,c
CH₂–CH₂F	26.7 (−18.2)
CH₂–CHF₂	26.7 (−14.5)
CH₂–CF₃	9.9 (−30.9)	1b^,e
CHF–CH₃	−17.0 (−52.3)
CHF–CH₂F	−21.1 (−54.6)
CHF–CHF₂	−23.4 (−56.1)
CHF–CF₃	−33.9 (−65.7)
CF₂–CH₃	−40.1 (−65.3)	96000b^,f
CF₂–CH₂F	−36.3 (−61.2)
CF₂–CHF₂	−42.9 (−66.3)
CF₂–CF₃	−49.7 (−72.6)	1160b^,g

a

Values in parentheses are corrected with zero point energy.

b

Ref. 1.

c

Ref. 14.

d

Ref. 17.

e

Ref. 16.

f

Ref. 15.

g

Ref. 6.