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. Author manuscript; available in PMC: 2009 Nov 5.
Published in final edited form as: J Am Chem Soc. 2008 Oct 9;130(44):14745–14754. doi: 10.1021/ja805067h

Table 2.

Self-Exchange and Pseudo Self-Exchange HAT Rate Constants and Deuterium Kinetic Isotope Effects for Transition Metal Coordination Complexes.a

Reaction ΔG° b kH (M−1 s−1) per H kH/kD Reference
RuIIimH+ RuIIIimc 0 (3.2 ± 0.3) ×105 1.5 ± 0.2 this work
[FeII(H2bim)3]2+ + [FeIII(H2bim)2(Hbim)]2+c 0 (9.7 ± 0.1) ×102 2.4 ± 0.3d 47
[FeII(H2bip)3]2+ + [FeIII(H2bip)2(Hbip)]2+c 0 (1.8± 0.3) ×103 1.6± 0.5 48
[RuIII(bpy)2(py)(OH)]2+ + [RuIV(bpy)2(py)O]2+e 0 (7.6 ± 0.4) ×104 1.2 ± 0.1 21a
[RuII(bpy)2(py)(OH2)] 2+ + [RuIV(bpy)2(py)O]2+e −2.5 (1.09± 0.02) × 105 16.1 ± 0.2 44
[RuII(tpy)(bpy)(OH2)]2+ + [RuIV(tpy)(bpy)O]2+e,f −2.5 (7.45 ± 0.55) × 105 11.4 ± 1.3 56
[RuII(bpy)2(py)(OH2)]2+ + [RuIII(tpy)(bpy)(OH)]2+e −1.3 (2.1 ± 0.1) ×105 5.8 ± 0.4 44
TpCl2OsIII(NH2Ph) + TpCl2OsIV(NHPh)c,g 0 (1.5 ± 1.0) ×10−3 ND 22
[VIV(4,4′-Me2bpy)2(O)(OH)]+ + [VV(4,4′-tBu2bpy)2(O)2]+c ~0 (6.5 ± 0.5) ×10−3 ND 21b
a

At 298 K.

b

kcal mol−1.

c

In MeCN.

d

At 324 K.

e

In H2O/D2O; tpy = 2,2′:6′,2″-terpyridine.

f

Other analogous Ru(H2O)/Ru(O) reactions, not shown in Table 2, have kH = 2.1 × 105 to 1.5 × 106 M−1 s−1 per H and kH/kD = 9.8–12.3 at 298 K.56

g

Tp = hydrotris(pyrazolyl)borate.