Table 4.
Comparison of CO and O2 Bimolecular Rates and Binding Constants for Select (Ligand)copper(I) Complexes, Hemocyanins (Hc), and Selected Hemesa
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compound or protein (solvent) | KCO (M−1) | KO2 (M−1) | kCO (M−1 s−1) | kO2 (M−1 s−1) | k−CO (s−1) | k−O2 (s−1) |
NMe2LCuI (THF) | 4.9 × 103 | 100 | 2.5 × 109 | 2.3 × 1011 | 5.0 × 105 | 2.3 × 109 |
ImLCuI (THF) | 2.4 × 103 | 17.4 | 2.8 × 109 | 3.4 × 1010 | 1.1 × 106 | 1.9 × 109 |
(TMPA)CuI (THF) | 1.2 × 104 | 15.4 | 1.9 × 109 | 1.3 × 109 | 1.6 × 105 | 1.3 × 108 |
(TMPA)CuI (EtCN) | 220 | 0.38 | 5.9 × 107 | 5.8 × 107 | 2.7 × 105 | 1.5 × 108 |
(tBuTMPA)CuI (THF)c | 1.7 | 1.6 × 108 | 9 × 107 | |||
(TMPA)CuI (EtCN) | 15.5 | 1.2 × 107 | ||||
(PV-TMPA)CuI (MeTHF) | 4.8 × 107 | |||||
(TMG3tren)CuI (MeTHF) | ~ 1 | 2.7 × 107 | 1.5 × 107 | |||
(LiPr)CuI (THF)d | 6.3 | 5.9 × 102 | 1.5 × 106 | |||
Cyt aa3 oxidase (CuB)e | 7 × 103 | 3.5 × 108 | 5 × 104 | |||
Cyt bo3 oxidase (cyt o3)f | 3.8 × 107 | |||||
Tt ba3g | 1 × 109 | |||||
myoglobin (human) | 2.6 × 107 | (0.74–117) × 104 | 7.6 × 105 | (1.4–25) × 107 | 0.022 | 22 |
hemoglobin (human) | 4.6 × 108 | (2.9–48) × 105 | 4.6 × 106 | (2.9–22) × 107 | 0.009 | 13.1 |
FeII-porphyrinatesh | 105 – 106 | 106 – 108 | ||||
Limulus Hc (arthropod) | (2.7–11.2) × 103 | (2.6–5.4) × 105 | (2–4.3) × 105 | (1.3–1.9) × 106 | 38–75 | 2.4–7.5 |
Busycon Hc (mollusk) | 220 × 103 | 1.8 × 105 | 7.7 × 105 | (1.1–2.2) × 106 | 3–4 | 6.5–11.5 |
Values correspond to 298 K, and for synthetic copper complexes, they have been extrapolated to this temperature from cryogenic measurements. See the following citations and references cited therein.691,940,977,1002,1003 Also see sections 2 and 3 in this review for further discussions regarding many of the synthetic complexes mentioned in this table.
MeTHF = 2-methyl tetrahydrofuran.
A TMPA ligand with 4-substituted (t-butyl) pyridyl donors.691
Extrapolated to 298 K from data in reference.1004
Binding to the o3 heme, E. coli bo3 ubiquinol oxidase.1005
Includes hemes such as picket fence, pocket, durene capped, chelated proto- or meso-, deutero- or tetraphenyl- porphyrin.