Cargando…

What Is the Nature of Supramolecular Bonding? Comprehensive NBO/NRT Picture of Halogen and Pnicogen Bonding in RPH(2)···IF/FI Complexes (R = CH(3), OH, CF(3), CN, NO(2))

We employ a variety of natural bond orbital (NBO) and natural resonance theory (NRT) tools to comprehensively investigate the nature of halogen and pnicogen bonding interactions in RPH(2)···IF/FI binary complexes (R = CH(3), OH, CF(3), CN, and NO(2)) and the tuning effects of R-substituents. Though...

Descripción completa

Detalles Bibliográficos
Autores principales: Jiao, Yinchun, Weinhold, Frank
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2019
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6600247/
https://www.ncbi.nlm.nih.gov/pubmed/31159347
http://dx.doi.org/10.3390/molecules24112090
_version_ 1783431073863041024
author Jiao, Yinchun
Weinhold, Frank
author_facet Jiao, Yinchun
Weinhold, Frank
author_sort Jiao, Yinchun
collection PubMed
description We employ a variety of natural bond orbital (NBO) and natural resonance theory (NRT) tools to comprehensively investigate the nature of halogen and pnicogen bonding interactions in RPH(2)···IF/FI binary complexes (R = CH(3), OH, CF(3), CN, and NO(2)) and the tuning effects of R-substituents. Though such interactions are commonly attributed to “sigma-hole”-type electrostatic effects, we show that they exhibit profound similarities and analogies to the resonance-type 3-center, 4-electron (3c/4e) donor-acceptor interactions of hydrogen bonding, where classical-type “electrostatics” are known to play only a secondary modulating role. The general 3c/4e resonance perspective corresponds to a continuous range of interatomic A···B bond orders (b(AB)), spanning both the stronger “covalent” interactions of the molecular domain (say, b(AB) ≥ ½) and the weaker interactions (b(AB) ˂ ½, often misleadingly termed “noncovalent”) that underlie supramolecular complexation phenomena. We show how a unified NBO/NRT-based description of hydrogen, halogen, pnicogen, and related bonding yields an improved predictive utility and intuitive understanding of empirical trends in binding energies, structural geometry, and other measurable properties that are expected to be manifested in all such supramolecular interaction phenomena.
format Online
Article
Text
id pubmed-6600247
institution National Center for Biotechnology Information
language English
publishDate 2019
publisher MDPI
record_format MEDLINE/PubMed
spelling pubmed-66002472019-07-16 What Is the Nature of Supramolecular Bonding? Comprehensive NBO/NRT Picture of Halogen and Pnicogen Bonding in RPH(2)···IF/FI Complexes (R = CH(3), OH, CF(3), CN, NO(2)) Jiao, Yinchun Weinhold, Frank Molecules Article We employ a variety of natural bond orbital (NBO) and natural resonance theory (NRT) tools to comprehensively investigate the nature of halogen and pnicogen bonding interactions in RPH(2)···IF/FI binary complexes (R = CH(3), OH, CF(3), CN, and NO(2)) and the tuning effects of R-substituents. Though such interactions are commonly attributed to “sigma-hole”-type electrostatic effects, we show that they exhibit profound similarities and analogies to the resonance-type 3-center, 4-electron (3c/4e) donor-acceptor interactions of hydrogen bonding, where classical-type “electrostatics” are known to play only a secondary modulating role. The general 3c/4e resonance perspective corresponds to a continuous range of interatomic A···B bond orders (b(AB)), spanning both the stronger “covalent” interactions of the molecular domain (say, b(AB) ≥ ½) and the weaker interactions (b(AB) ˂ ½, often misleadingly termed “noncovalent”) that underlie supramolecular complexation phenomena. We show how a unified NBO/NRT-based description of hydrogen, halogen, pnicogen, and related bonding yields an improved predictive utility and intuitive understanding of empirical trends in binding energies, structural geometry, and other measurable properties that are expected to be manifested in all such supramolecular interaction phenomena. MDPI 2019-05-31 /pmc/articles/PMC6600247/ /pubmed/31159347 http://dx.doi.org/10.3390/molecules24112090 Text en © 2019 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Jiao, Yinchun
Weinhold, Frank
What Is the Nature of Supramolecular Bonding? Comprehensive NBO/NRT Picture of Halogen and Pnicogen Bonding in RPH(2)···IF/FI Complexes (R = CH(3), OH, CF(3), CN, NO(2))
title What Is the Nature of Supramolecular Bonding? Comprehensive NBO/NRT Picture of Halogen and Pnicogen Bonding in RPH(2)···IF/FI Complexes (R = CH(3), OH, CF(3), CN, NO(2))
title_full What Is the Nature of Supramolecular Bonding? Comprehensive NBO/NRT Picture of Halogen and Pnicogen Bonding in RPH(2)···IF/FI Complexes (R = CH(3), OH, CF(3), CN, NO(2))
title_fullStr What Is the Nature of Supramolecular Bonding? Comprehensive NBO/NRT Picture of Halogen and Pnicogen Bonding in RPH(2)···IF/FI Complexes (R = CH(3), OH, CF(3), CN, NO(2))
title_full_unstemmed What Is the Nature of Supramolecular Bonding? Comprehensive NBO/NRT Picture of Halogen and Pnicogen Bonding in RPH(2)···IF/FI Complexes (R = CH(3), OH, CF(3), CN, NO(2))
title_short What Is the Nature of Supramolecular Bonding? Comprehensive NBO/NRT Picture of Halogen and Pnicogen Bonding in RPH(2)···IF/FI Complexes (R = CH(3), OH, CF(3), CN, NO(2))
title_sort what is the nature of supramolecular bonding? comprehensive nbo/nrt picture of halogen and pnicogen bonding in rph(2)···if/fi complexes (r = ch(3), oh, cf(3), cn, no(2))
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6600247/
https://www.ncbi.nlm.nih.gov/pubmed/31159347
http://dx.doi.org/10.3390/molecules24112090
work_keys_str_mv AT jiaoyinchun whatisthenatureofsupramolecularbondingcomprehensivenbonrtpictureofhalogenandpnicogenbondinginrph2ifficomplexesrch3ohcf3cnno2
AT weinholdfrank whatisthenatureofsupramolecularbondingcomprehensivenbonrtpictureofhalogenandpnicogenbondinginrph2ifficomplexesrch3ohcf3cnno2