Through-bond orbital coupling, the parity rule, and the design of 'superbridges' which exhibit greatly enhanced electronic coupling: A natural bond orbital analysis

Journal of the American Chemical Society

Volumn 119, Issue 23, 1997, Pages 5355-5365

  Paddon Row, Michael N ^a   Shephard, Michael J ^a  

^a UNIVERSITY OF NEW SOUTH WALES   (Australia)

Author keywords

[No Author keywords available]

Indexed keywords

ARTICLE; BINDING AFFINITY; BINDING SITE; CHEMICAL REACTION KINETICS; ELECTROCHEMISTRY; MOLECULAR INTERACTION;

EID: 0030859229     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja964132x     Document Type: Article

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58. The number of single-jump and double-jump pathways given in the text ignores any retracing pathways and pathways involving the terminal bridge a bonds. See also ref 40.
59. Another possible requirement for constructive interference may be that coupling through interrelay pathways involving an odd number of interrelay jumps is insignificant. However, this requirement implies that coupling through interrelay pathways involving an even number of interrelay jumps would also be negligible. Hence, the coupling through a bridge meeting this requirement should not display any significant interrelay interference effects at all.
60. s symmetric dienes of Scheme 3, n refers to the length of the shorter main relay.
61. 6 (Scheme 1), have a negligible influence on the π splittings, and so, for convenience, they were retained in model C.
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63. s symmetric dienes 5(n) and 9(n).
64. 2, arising from the first jump in pathway (4c) (both types of jumps ending at the same point on the main relay) will always have opposite signs.
65. That the ΔE(π) values for the two homoallylic pathways (4b) and (4e) have opposite signs is the consequence of geometrically imposed different modes of orbital overlap that exist between the π NBO and the homoallylic bonds. In the case of pathway (4b) the π NBO overlaps with the main lobe of the upper relay homoallylic C-C σ NBO, whereas in the case of pathway (4e) the π/σ overlap involves the tail of the lower relay homoallylic C-C σ NBO.
66. i, calculated for a coupling pathway, to be odd (even), even though the splitting induced by that pathway follows a natural (inverted) sequence.
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68. For 4(n) the π*-tuned ΔE(π*) values are nearly twice as large as their respective HF/3-21G ΔE(π) values (Table 1). However, this is due to the fact that the absolute magnitude of the interaction matrix element between the π* NBO and the allylic C-C σ NBO (1.53 eV) is larger than that between the π NBO and the same σ NBO (1.08 eV).
69. 2 symmetric dienes of Scheme 3 is due to interrelay coupling pathways since the π orbitals in these systems are barely coupled to each other through the same main relay.
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