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. Author manuscript; available in PMC: 2012 Aug 10.
Published in final edited form as: J Am Chem Soc. 2011 Jul 19;133(31):11880–11883. doi: 10.1021/ja2040909

Table 2.

Second-order rate constants (k2) observed in reactions of FeIV=O complexes with substrates.

Complex a k2 [M−1 s−1] in CH3CN solution at −30°C b
CHD DHA PPh3
7 18 57 c
2 d 1.2 0.090 1.1
8 d 1.3 2.0 1.5
9 d 0.018 0.016 0.22
10 e 94 310 c
a

[FeIV(O)(N4Py)]2+ (8, N4Py = bis(2-pyridylmethyl)-bis(2-pyridyl)-methylamine), [FeIV(O)(TMC)(CH3CN)]2+ (9, TMC = 1,4,8,11-tetramethylcyclam), [FeIV(O)(Me3NTB)]2+ (10, Me3NTB = tris((N-methyl-benzimidazol-2-yl)methyl)amine)).

b

Reaction kinetics for 2, 8 and 9 were measured using 1.0 mM complex. For 7 the larger rates of reaction required the use of 0.1–0.2 mM complex and similarly reduced concentrations of substrate.

c

This reaction was too fast for measurement of kobs.

d

Kinetic data from reference 5a.

e

Kinetic data at −40 °C taken from reference 17.