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58
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0038418719
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note
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TD-DFT calculations on a similar MeCbl model using more typical C-H bond lengths of 1.08 Å were performed, and results showed no significant differences in MO composition or transition state energies as compared to the results from the model with shorter C-H bond lengths.
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0004247468
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Banerjee, R., Ed.; Wiley: New York
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12; Banerjee, R., Ed.; Wiley: New York, 1999), but analysis of the corresponding transitions is beyond the scope of this study.
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12
-
-
Pratt, J.M.1
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86
-
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0038080155
-
-
note
-
The fold angle φ is described by the angle between the planes formed by N21-C4-C5-C6-N22-C9-C10 and C10-C11-N23-C14-C15-C16-N24. For AdoCbl, φ is 13.3° (see ref 55), and for MeCbl, φ is 14,7° (see ref 54).
-
-
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87
-
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0029805698
-
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Dong, S. L.; Padmakumar. R.; Banerjee, R.; Spiro, T. G. J. Am. Chem. Soc. 1996, 118, 9182-9183.
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88
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0001195081
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Dong, S. L.; Padmakumar, R.; Banerjee, R.; Spiro, T. G. Inorg. Chim. Acta 1998, 270, 392-398.
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89
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0032582097
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Dong, S. L.; Padmakumar, R.; Maiti, N.; Banerjee, R.; Spiro, T. G. J. Am. Chem. Soc. 1998, 120, 9947-9948.
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0000472226
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0001726298
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93
-
-
0038080154
-
-
note
-
The replacement of the DMB by an imidazole in the Cbl models requires no change in the conformation of the corrin ring, as the coordinates for all corrin atoms are taken directly from the X-ray data. As such, the frozen macrocycle maintains all steric effects imposed by outer ring substituents including the nucleotide loop and DMB, which are not explicitly included in our models.
-
-
-
-
95
-
-
0038418716
-
-
note
-
+ are presented in Figures S5 and S7, respectively.
-
-
-
-
96
-
-
0037742633
-
-
note
-
Note that the x and y axes are rotated by 45° about z from their usual orientations along the metal-ligand bonds. The designation of Co 3d orbitals contributing to Cbl MOs reflects this rotation.
-
-
-
-
97
-
-
0038080152
-
-
note
-
The percentages listed give the contributions of individual one-electron excitations required to model the charge distribution in the corresponding excited state. It is expected that those excitations with donor and acceptor MOs composed of similar atomic orbitals are the dominant intensity contributors to the overall transition.
-
-
-
-
98
-
-
0038418717
-
-
note
-
+ (see Figure S5 and Table S 13).
-
-
-
-
99
-
-
0037742634
-
-
note
-
The relatively high intensity of this transition derives from the fact that the corrin C and N 2p orbitals contributing to the donor MO (#114) are also the main contributors to the acceptor MO (#117).
-
-
-
-
102
-
-
0003968035
-
-
Tackett, S. L.; Collat, J. W.; Abbott, J. C. Biochemistry 1963, 2, 919-923.
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106
-
-
0038756784
-
-
note
-
+ as compared to that for AdoCbl are not inconsistent with our computations that suggest a similar Co-C bond strength in the two species, in nice agreement with published RR and IR data.
-
-
-
-
109
-
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0024832385
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