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Akiba, K., Moriyama, Y., Mizozoe, M., Inohara, H., Nishii, T., Yamamoto, Y., Minoura, M., Hashizume, D., Iwasaki, F., Takagi, N., Ishimura, K. and Nagase, S. (2005) Synthesis and Characterization of Stable Hypervalent Carbon Compounds (10-C-5) Bearing a 2,6-bis(p-Substituted Phenyloxymethyl)Benzene Ligand. Journal of the American Chemical Society, 127, 5893-5901. http://dx.doi.org/10.1021/ ja043802t

has been cited by the following article:

• TITLE: Three-Center Configuration with Four,Three, and Two Electrons for Carbon,Boron, Hydrogen, and Halogen Exchange. A Model and Theoretical Study with Experimental Evidence

  AUTHORS: Henk M. Buck

  KEYWORDS: Three-Center Configuration, Frozen Transition State, Molecular Drone, Enigma, Classical and Nonclassical 2-Norbornyl Cation

  JOURNAL NAME: Open Journal of Physical Chemistry, Vol.4 No.2, April 21, 2014

  ABSTRACT: The introduction of specific sites in organic frames for accommodation of various modes of bonding has been focused on reaction types which are described by using different theoretical models with or without a definite experimental proof. In this study three-center four-, three-, and two-electron systems based on carbon-, boron-, hydrogen-, and halogen exchange are under consideration. Based on the number of electrons in the transition state or transition complex it is shown that all transfer or exchange reactions share the same ratio numbers expressed as the quotient of the transitional bond distance under investigation and its normal bond length. With X-ray data of model systems it was even possible to give the ratio numbers for a three-center four-electron configuration experimental support with additional ab initio data. Furthermore a novel model type of substitution in organic chemistry is introduced through electrophilic insertion, informative for enzyme-substrate interactions based on the lock-and-key model. Reactions based on a three-center two-electron configuration mostly follow a nonlinear transition. In this alignment there will be a pursuit of cyclization for stabilization via homoaromaticity as homocyclopropenyl cation. The molecular dynamics of such a process is discussed based on recent X-ray crystallographic data of the symmetrically bridged, nonclassical geometry of the 2-norbornyl cation. In the present paper the focus is aimed at the transition intermediate of the (classical) 2-norbornyl cation involved in the isomerization into the nonclassical geometry. This model description is compared with a simple molecular rearrangement of the 1-propyl cation into the corner-protonated cyclopropane using the ab initio data. The exclusivity of the former isomerization compared with the latter one could be unambiguously demonstrated by the invention that theintramolecularelectron shift can be expressed in a linear relationship between the concerned electron-donating and accepting bond lengths. Finally, the fluor transitions as divalent atoms in a three-center two-electron configuration are described. The role of fluor in comparison with the other halogens is striking. The attention was focused on an excellent correspondence between the recent chemical and theoretical evidence for a symmetrical fluoronium ionin solution. Simple dialkylfluoroniumions in contrast to the other halonium ions are not present in solution. Although the geometry of the fluoronium ion theoretically can be described as a real minimum, the C-F-C angle of 120° is apparently the borderline transition for dissociation in C+ and F-C.