. Author manuscript; available in PMC: 2011 Sep 14.

Published in final edited form as: Biochemistry. 2010 Sep 14;49(36):7902–7912. doi: 10.1021/bi1009375

Table 4.

Class II Substrates of H_peroxo: Correlation Between k_obs and BDE

Substrate^a	k_obs (M^-1 s^-1)	D(R⁺H^-) (kcal/mol)^b	-ΔG_hydride(R⁺)s (kcal/mol)^c	D(RH) (kcal/mol)^d
(CH₃CH₂)₂O^e	17 ± 1	214	94.8	93.0
CH₃CH₂OH	12.13 ± 0.01	231.9	110.9	94.6
CH₃OH	2.4 ± 0.6	255	131.8	96.06

D(R⁺H^-) and D(RH) are given for the bolded C–H bond. For diethyl ether, this position is the sole C–H bond activated by sMMO in steady state assays (26).

Data from (64).

Calculated using -ΔG_hydride (R⁺)s = 0.904D(R⁺H^-) – 98.7 kcal/mol from (65). This relationship was originally derived for aromatic molecules in acetonitrile and DMSO, but should provide a good approximation for non-aromatic systems in aqueous solution.

Data from (47).

Data from (26).