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xy undergoes a σ bond with the porphyrin and can therefore be classified as an "e" orbital.
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81
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33645849948
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note
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2u〈81〉.
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82
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33645870513
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84
-
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33645893329
-
-
note
-
2] (cf. Figure 2), these signals are observed at 8.97 ppm, which is close to the value of ∼8.1 ppm for 2. In contrast, these hydrogens show a stronger paramagnetic shift to 5.95 ppm in 1. Correspondingly, the calculated spin densities on the pyrrole hydrogens are 2-4 times larger in 1 than they are in 2.
-
-
-
-
85
-
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36749114016
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Utterback, S. G.; Doetschman, D. C.; Szumowski, J.; Rizos, A. K. J. Chem. Phys. 1983, 78, 5874-5880.
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0002312013
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Dolphin, D., Ed.; Academic Press: New York
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Gouterman, M.1
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89
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33645841444
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Lever, A. B. P., Gray, H. B., Eds.; Addison-Wesley: Reading, MA
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(b) Spiro, T. G. In Iron Porphyrins; Lever, A. B. P., Gray, H. B., Eds.; Addison-Wesley: Reading, MA, 1983; Part 2.
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Spiro, T.G.1
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90
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0442326625
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(c) Egawa, T.; Suzuki, N.; Dokoh, T.; Higuchi, T.; Shimada, H.; Kitagawa, T.; Ishimura, Y. J. Phys. Chem. A 2004, 108, 568-577.
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Ishimura, Y.7
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92
-
-
33645893875
-
-
note
-
Because of a disorder in the crystal, the experimental structure of 1 in ref 27 has a planar TPP ring. This, however, is certainly not the case in the actual complex and, correspondingly, the INDO/S-CI calculations on this structure lead to a wrong ground state. Therefore, the conformation of the TPP ring from the crystal structure of 2 was applied in the TD-DFT calculation for 1. This contributes to the incorrect calculation of the Soret shift.
-
-
-
-
93
-
-
33645872516
-
-
note
-
z2 in 1 (induced by the out-of-plane displacement of iron).
-
-
-
-
94
-
-
33645880886
-
-
note
-
v cannot be calculated with these methods.
-
-
-
-
96
-
-
0015238929
-
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(b) Hoard, J. L. Science 1971, 174, 1295.
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99
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0029168628
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Hodgson, K.O.6
Solomon, E.I.7
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100
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1942456778
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0033520701
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14944339704
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Saraste, M.7
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