Interconversion between Planar-Triangle, Trigonal-Pyramid and Tetrahedral Configurations of Boron (B(OH)3 -B(OH)4- ), Carbon (CH3+ -CH3X) and for the Group 15 Elements as Nitrogen (NH3-NH4+ ). A Modelling Description with Ab Initio Results and Pressure-Induced Experimental Evidence

DOI: 10.4236/ojpc.2015.51001   PDF   HTML   XML   3,615 Downloads   4,108 Views   Citations


Recently a mechanistic understanding of the pressure-and/or temperature-induced coordination change of boron in a borosilicate glass has been demonstrated by Edwards et al. In situ high-pressure 11B solid-state NMR spectroscopy has been used in combination with ab initio calculations in order to obtain insight in the molecular geometry for the pressure-induced conversion. The results indicate a deformation of the B(OH)3 planar triangle, under isotropic stress, into a trigonal pyramid that serves as a precursor for the formation of a tetrahedral boron configuration. From our point of view, the deformation controlling the out-of-plane transition of boron accompanied with a D3h into C3v geometric change is an interesting transformation because it matches with our molecular description based on Van’t Hoff modelling for the tetrahedral change of carbon in CH3X by substitution of X with nucleophiles via a trigonal bipyramid state in which the transferred carbon is present as a methyl planar triangle “cation”. Van’t Hoff modelling and ab initio calculations have been also applied on the dynamics of the out-of-plane geometry of a transient positively charged carbon in a trigonal pyramidal configuration into a planar trivalent carbon cation. Finally the same model is also used for the C3v trigonal pyramidal configurations as NH3 of the group 15 elements in their nucleophilic abilities.

Share and Cite:

Buck, H. (2015) Interconversion between Planar-Triangle, Trigonal-Pyramid and Tetrahedral Configurations of Boron (B(OH)3 -B(OH)4- ), Carbon (CH3+ -CH3X) and for the Group 15 Elements as Nitrogen (NH3-NH4+ ). A Modelling Description with Ab Initio Results and Pressure-Induced Experimental Evidence. Open Journal of Physical Chemistry, 5, 1-8. doi: 10.4236/ojpc.2015.51001.

Conflicts of Interest

The authors declare no conflicts of interest.


[1] Buck, H.M. (2008) A Combined Experimental, Theoretical, and Van’t Hoff Model Study for Identity Methyl, Proton, Hydrogen Atom, and Hydride Exchange Reactions. Correlation with Three-Center Four-, Three-, and Two-Electron Systems. International Journal of Quantum Chemistry, 108, 1601-1614.
[2] Buck, H.M. (2010) A Linear Three-Center Four Electron Bonding Identity Nucleophilic Substitution at Carbon, Boron, and Phosphorus. A Theoretical Study in Combination with Van’t Hoff Modeling. International Journal of Quantum Chemistry, 110, 1412-1424.
[3] Buck, H.M. (2011) A Model Investigation of ab Initio Geometries for Identity and Nonidentity Substitution with Three-Center Four- and Three-Electron Transition States. International Journal of Quantum Chemistry, 111, 2242- 2250.
[4] Buck, H.M. (2012) Mechanistic Models for the Intramolecular Hydroxycarbene-Formaldehyde Conversion and Their Intermolecular Interactions: Theory and Chemistry of Radicals, Mono-, and Dications of Hydroxycarbene and Related Configurations. International Journal of Quantum Chemistry, 112, 3711-3719.
[5] Buck, H.M. (2013) An Adjusted Model for Simple 1,2-Dyotropic Reactions. Ab Initio MO and VB Considerations. Open Journal of Physical Chemistry, 3, 119-125.
[6] Buck, H.M. (2014) Three-Center Configuration with Four, Three, and Two Electrons for Carbon, Hydrogen, and Halogen Exchange. A Model and Theoretical Study with Experimental Evidence. Open Journal of Physical Chemistry, 4, 33-43.
[7] Yamashita, M., Yamamoto, Y., Akiba, K., Hashizume, D., Iwasaki, F., Takagi, N. and Nagase, S. (2005) Syntheses and Structures of Hypervalent Pentacoordinate Carbon and Boron Compounds Bearing an Anthracene Skeleton. Elucidation of Hypervalent Interaction Based on X-Ray Analysis and DFT Calculation. Journal of the American Chemical Society, 127, 4354-4371.
[8] Bento, A.P. and Bickelhaupt, F.M. (2008) Nucleophilicity and Leaving Group Ability in Frontside and Backside SN2 Reactions. Journal of Organic Chemistry, 73, 7290-7299.
[9] Bento, A.P. and Bickelhaupt, F.M. (2008) Frontside versus Backside SN2 Substitution of Group 14 Atoms. Origin of Reaction Barriers and Reasons for Their Absence. Chemistry—An Asian Journal, 3, 1783-1792.
[10] Glukhovtsev, M.N., Pross, A. and Radom, L. (1995) Gas-Phase Identity SN2 Reactions of Halide Anions with Methyl Halides: A High-Level Computational Study. Journal of the American Chemical Society, 117, 2024-2032.
[11] Edwards, T., Endo, T., Walton, J.H. and Sen, S. (2014) Observation of the Transition State for Pressure-Induced BO3 → BO4 Conversion in Glass. Science, 345, 1027-1029.
[12] Taylor, M.J., Grigg, J.A. and Rickard, C.E.F. (1992) The Structure of the Cage-Like Complex Anion Formed by Sodium Borate and 1,1,1-Tris(Hydroxymethyl)Ethane. Polyhedron, 11, 889-892.
[13] Dewar, M.J.S. (1969) The Molecular Orbital Theory of Organic Chemistry. Chapter 8, McGraw Hill Book Company, New York.
[14] Fitzgibbons, T.C., Guthrie, M., Xu, E.S., Crespi, V.H., Davidowski, S.K., Cody, G.D., Alem, N. and Badding, J.V. (2014) Benzene-Derived Carbon Nanothreads. Nature Materials, 14, 43-47.
[15] Jung, M.E. and Lee, G.S. (2014) Synthesis of Highly Substituted Adamantanones from Bicyclo[3.3.1]Nonanes. Journal of Organic Chemistry, 79, 10547-10552.
[16] Harding, M.E., Gauss, J. and von Ragué Schleyer, P. (2011) Why Benchmark-Quality Computations Are Needed to Reproduce 1-Adamantyl Cation NMR Chemical Shifts Accurately. Journal of Physical Chemistry A, 115, 2340-2344.
[17] Rasul, G., Olah, G.A. and Prakash, G.K.S. (2010) Density Functional Theory Study of Adamantanediyl Dications and Protio-Adamantyl Dications . Proceedings of the National Academy of Sciences of the United States of America, 101, 10868-10871.
[18] Schreiner, P.R., Chernish, L.V., Gunchenko, P.A., Tikhonchuk, E.Y., Hausmann, H., Serafin, M., Schlecht, S., Dahl, J.E.P., Carlson, R.M.K. and Fokin, A.A. (2011) Overcoming Lability of Extremely Long Alkane Carbon-Carbon Bonds through Dispersion Forces. Nature, 477, 308-311.
[19] Buck, H.M. (2000) Symmetry Restrictions as Starting Point for the Determination of Geometric Representations and the Dynamics of Cyclic π Systems. International Journal of Quantum Chemistry, 77, 641-650.<641::AID-QUA5>3.0.CO;2-R
[20] Buck, H.M. (2011) DNA Systems for B-Z Transition and Their Significance as Epigenetic Model: The Fundamental Role of the Methyl Group. Nucleosides, Nucleotides and Nucleic Acids, 30, 918-944.
[21] Buck, H.M. (2013) A Conformational B-Z DNA Study Monitored with Phosphatemethylated DNA as a Model for Epi- Genetic Dynamics Focused on 5-(Hydroxy)Methylcytosine. Journal of Biophysical Chemistry, 4, 37-46.

comments powered by Disqus

Copyright © 2020 by authors and Scientific Research Publishing Inc.

Creative Commons License

This work and the related PDF file are licensed under a Creative Commons Attribution 4.0 International License.