Table 1.1

Selected geometric parameters [O1–O1′ bond distances r(O1–O1′), C2–C4 bond distances r(C2–C4) and C2-O1–O1′–C2′ dihedral angles δ(C2–O1–O1′–C2′)] of RC(O)O–OC(O)R peroxides determined with MP2/DZP geometry optimization, and bond orders (BOs) of O1–O1′ and C2–C4 calculated with the RHF/DZP method for the optimized geometry.

Rr(O1–O1′)/ÅBO(O1–O1′)r(C2–C4)/ÅaBO(C2–C4)aδ(C2–O1–O1′–C2′)/°
CH3 1.449 0.931 1.507 1.069 77.5 
CH2F 1.452 0.934 1.520 1.036 79.1 
CHF2 1.452 0.934 1.534 0.998 80.4 
CF3 1.448 0.938 1.545 0.990 80.3 
CH2–CH3 1.452 0.932 1.512 1.043 77.0 
CH2–CH2F 1.453 0.932 1.514 1.026 76.8 
CH2–CHF2 1.452 0.933 1.510 1.024 76.7 
CH2–CF3 1.450 0.935 1.514 1.007 79.1 
CHF–CH3 1.449 0.935 1.522 0.998 74.7 
CHF–CH2F 1.449 0.936 1.521 0.986 73.9 
CHF–CHF2 1.448 0.941 1.521 0.999 77.0 
CHF–CF3 1.448 0.938 1.528 0.986 74.6 
CF2–CH3 1.451 0.939 1.539 0.984 75.3 
CF2–CH2F 1.453 0.939 1.540 0.961 79.3 
CF2–CHF2 1.450 0.940 1.542 0.971 77.3 
CF2–CF3 1.449 0.941 1.542 0.974 76.0 
H 1.454 0.808   80.9 
Hydrogen peroxide 1.460 0.879   115.0b 
Rr(O1–O1′)/ÅBO(O1–O1′)r(C2–C4)/ÅaBO(C2–C4)aδ(C2–O1–O1′–C2′)/°
CH3 1.449 0.931 1.507 1.069 77.5 
CH2F 1.452 0.934 1.520 1.036 79.1 
CHF2 1.452 0.934 1.534 0.998 80.4 
CF3 1.448 0.938 1.545 0.990 80.3 
CH2–CH3 1.452 0.932 1.512 1.043 77.0 
CH2–CH2F 1.453 0.932 1.514 1.026 76.8 
CH2–CHF2 1.452 0.933 1.510 1.024 76.7 
CH2–CF3 1.450 0.935 1.514 1.007 79.1 
CHF–CH3 1.449 0.935 1.522 0.998 74.7 
CHF–CH2F 1.449 0.936 1.521 0.986 73.9 
CHF–CHF2 1.448 0.941 1.521 0.999 77.0 
CHF–CF3 1.448 0.938 1.528 0.986 74.6 
CF2–CH3 1.451 0.939 1.539 0.984 75.3 
CF2–CH2F 1.453 0.939 1.540 0.961 79.3 
CF2–CHF2 1.450 0.940 1.542 0.971 77.3 
CF2–CF3 1.449 0.941 1.542 0.974 76.0 
H 1.454 0.808   80.9 
Hydrogen peroxide 1.460 0.879   115.0b 
a

C2–C4 is the C–C bond adjacent to the O–O group (see Figure 1.1a for atom labeling).

b

H–O–O–H dihedral angle, i.e. δ(H–O–O–H).

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