Table 1. Canonical Rate Coefficients at T = 298.15 K (in Unit s–1) for the Model Complexes (All in the Triplet State) in All Three Levels of Theorya.
| complex | D (kcal/mol) | l = 0 | l2 = ⟨l2⟩ | variable l | DB30 | RRKM |
|---|---|---|---|---|---|---|
| (MetO)2 | 3.32 | 1.45 × 1010 | 3.58 × 1010 | 7.56 × 1010 | 6.21 × 1013 | 9.72 × 1013 |
| (EtO)2 | 5.61 | 2.80 × 1008 | 8.08 × 1008 | 2.57 × 1009 | 1.16 × 1011 | 1.89 × 1012 |
| (ProO)2 | 4.70 | 1.04 × 1009 | 3.18 × 1009 | 8.87 × 1009 | 1.11 × 1013 | 5.20 × 1013 |
| (AceO)2 | 6.85 | 2.99 × 1007 | 1.01 × 1008 | 1.51 × 1009 | 3.97 × 1011 | 2.48 × 1011 |
| (ButO)2 | 4.55 | 1.05 × 1009 | 3.05 × 1009 | 9.03 × 1009 | 9.71 × 1013 | 8.24 × 1013 |
| R,R-(BuOHO)2 | 13.42 | 5.72 × 1002 | 2.26 × 1003 | 2.96 × 1004 | 7.48 × 1009 | |
| R,S-(BuOHO)2 | 8.02 | 3.72 × 1006 | 1.34 × 1007 | 8.10 × 1007 | 6.29 × 1013 | |
| R-alkoxy,R-nitroxy-α-pin | 10.71 | 2.50 × 1004 | 1.36 × 1005 | 2.42 × 1006 | ||
| R-alkoxy,S-nitroxy-α-pin | 10.18 | 5.73 × 1004 | 2.21 × 1005 | 2.43 × 1006 | ||
| S-alkoxy,R-nitroxy-α-pin | 18.19 | 1.07 × 10–01 | 4.84 × 10–01 | 2.67 × 1001 | ||
| S-alkoxy,S-nitroxy-α-pin | 10.83 | 2.11 × 1004 | 8.85 × 1004 | 1.45 × 1006 | ||
| (α-pin-O3–RO)2 | 13.682 | 2.23 × 1002 | 1.01 × 1003 | 3.67 × 1004 | ||
| MetO-EtO | 4.570 | 1.67 × 1009 | 4.56 × 1009 | 1.20 × 1010 | ||
| MetO-ProO | 3.704 | 6.25 × 1009 | 1.78 × 1010 | 4.48 × 1010 | ||
| MetO-AceO | 3.336 | 8.69 × 1009 | 2.48 × 1010 | 5.99 × 1010 | ||
| MetO-ProOHO | 7.872 | 7.95 × 1006 | 2.99 × 1007 | 2.01 × 1008 | 5.55 × 1011 | 6.69 × 1010 |
| MetO-BuOHO | 6.993 | 2.94 × 1007 | 1.25 × 1008 | 1.02 × 1009 | ||
| EtO-ProO | 5.221 | 5.02 × 1008 | 1.50 × 1009 | 4.67 × 1009 | ||
| EtO-AceO | 5.983 | 1.48 × 1008 | 4.90 × 1008 | 2.05 × 1009 | ||
| EtO-ProOHO | 9.486 | 5.08 × 1005 | 1.87 × 1006 | 1.44 × 1007 | ||
| EtO-BuOHO | 8.617 | 1.86 × 1006 | 7.62 × 1006 | 6.77 × 1007 | ||
| ProO-AceO | 5.835 | 1.59 × 1008 | 5.01 × 1008 | 1.90 × 1009 | ||
| ProO-ProOHO | 8.980 | 1.02 × 1006 | 3.62 × 1006 | 2.08 × 1007 | ||
| ProO-BuOHO | 8.326 | 2.69 × 1006 | 1.01 × 1007 | 5.97 × 1007 | ||
| AceO-ProOHO | 9.591 | 3.43 × 1005 | 1.23 × 1006 | 7.91 × 1006 | ||
| AceO-BuOHO | 9.898 | 1.99 × 1005 | 7.64 × 1005 | 5.61 × 1006 |
a
DB = detailed balance. The dissociation energies are presented for comparison, as they are clearly the most important parameters determining the dissociation rate. The number of decimals used for the dissociation energies is kept the same from the original sources. As seen in the last column on the right, dissociation rates calculated assuming detailed balance of association and dissociation overestimate the dissociation rate up to unphysical values. This is pointed out in the original article as well.30