Are Various σ‐Hole Bonds Steered by the Same Mechanisms?

Grabowski, Sławomir J.; Sokalski, W. Andrzej

doi:10.1002/cphc.201700224

Cited by 69 publications

(69 citation statements)

References 76 publications

(161 reference statements)

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“…For weak hydrogen bonds the electrostatic energy usually overwhelms the Pauli repulsion thus the Heitler–London term is negative. The similar results were found recently for a broader sample of σ‐hole bonds where the positive Heitler–London interaction energy term increases with the increase of the strength of interaction …”

Section: Resultssupporting

confidence: 90%

Two faces of triel bonds in boron trihalide complexes

Grabowski

2017

J Comput Chem

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The N⋅⋅⋅B triel bonds in complexes of boron trihalides, BX (X = F, Cl, Br, and I), with species acting as Lewis bases through the nitrogen center, NH , N , and HCN, are analyzed theoretically (MP2/aug-cc-pVTZ calculations). It is confirmed that stronger Lewis acid properties of the boron center are observed for the BCl moiety than for the BF one in complexes with the strong Lewis base (NH ); while the opposite order is observed for complexes with the weak Lewis base (N ). The BX NCH complexes (for X = Cl, Br, and I) are characterized by two tautomeric forms and by two corresponding N⋅⋅⋅B distances, the shorter one possesses characteristics of the covalent bond. In a case of the BF NCH complex one energetic minimum is observed. Ab initio calculations are supported by an analysis of molecular electrostatic potentials (EPs) and electron density distributions. The quantum theory of 'atoms in molecules' and the decomposition of the energy of interaction are applied. The aforementioned acidity orders as well as the existence of two tautomers for some of complexes result partly from the electrostatic interactions' balance; the EP distribution is different for the BF species than for the other BX species where X = Cl, Br, and I. © 2017 Wiley Periodicals, Inc.

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Section: Resultssupporting

confidence: 90%

Two faces of triel bonds in boron trihalide complexes

Grabowski

2017

J Comput Chem

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“…Positive values of Δ E HL were also observed for the broader spectrum of strong σ‐hole bonds analyzed recently . The latter values were accompanied by the negative H BCP values for the majority of complexes analyzed; only for the weakest interactions for which Δ E HL is positive but close to zero are positive H BCP values observed …”

Section: Resultssupporting

confidence: 57%

“…It was found, for the hydrogen‐bonded systems, that Δ E HL is accompanied by a negative topological parameter H BCP , and sometimes even by a negative value of ∇ 2 ρ BCP of the corresponding BCP . Positive values of Δ E HL were also observed for the broader spectrum of strong σ‐hole bonds analyzed recently . The latter values were accompanied by the negative H BCP values for the majority of complexes analyzed; only for the weakest interactions for which Δ E HL is positive but close to zero are positive H BCP values observed …”

Section: Resultsmentioning

confidence: 70%

π⋅⋅⋅H⁺⋅⋅⋅π Hydrogen Bonds and Their Lithium and Gold Analogues: MP2 and CASPT2 Calculations

Grabowski

Ruipérez

2017

ChemPhysChem

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Molecular systems in which two simple π-electron species, acetylene and ethylene, are linked by a cation located between them are analyzed in this study. In particular, the C H ⋅⋅⋅M ⋅⋅⋅C H , C H ⋅⋅⋅M ⋅⋅⋅C H , and C H ⋅⋅⋅M ⋅⋅⋅C H complexes (M =H , Li , Au ) are calculated with the use of MP2 and CASPT2 methods. The Quantum Theory of Atoms in Molecules (QTAIM), energy decomposition analysis (EDA), and Natural Bond Orbital (NBO) approaches are applied to deepen the understanding of the nature of M ⋅⋅⋅π interactions in these complexes. It is found that the interactions in gold and proton complexes are characterized by at least partial covalency, whereas interactions in lithium complexes are rather electrostatic in nature.

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“…This sort of bond can, for example, be considered a preliminary step in the very common S N 2 reaction. [43][44][45][46] There has also been some consideration of the rather unusual bases carbenes [47,48] or π-systems [33] as tetrel bond acceptors. [16][17][18][19][20][21] There is a rapidly growing literature [22][23][24][25][26][27] that has provided a wealth of insights into the chemical and physical phenomena that underlie tetrel bonds.…”

Section: Introductionmentioning

confidence: 99%

Hexacoordinated Tetrel‐Bonded Complexes between TF₄ (T=Si, Ge, Sn, Pb) and NCH: Competition between σ‐ and π‐Holes

et al. 2019

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In order to accommodate the approach of two NCH bases, a tetrahedral TF 4 molecule (T=Si, Ge, Sn, Pb) distorts into an octahedral structure in which the two bases can be situated either cis or trans to one another. The square planar geometry of TF 4 , associated with the trans arrangement of the bases, is higher in energy than its see-saw structure that corresponds to the cis trimer. On the other hand, the square geometry offers an unobstructed path of the bases to the π-holes above and below the tetrel atom and hence enjoys a higher interaction energy than is the case for the σ-holes approached by the bases in the cis arrangement. When these two effects are combined, the total binding energies are more exothermic for the cis than for the trans complexes. This preference amounts to some 3 kcal mol À 1 for Sn and Pb, but is amplified for the smaller tetrel atoms.[a] M. Michalczyk, Dr.

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Are Various σ‐Hole Bonds Steered by the Same Mechanisms?

Cited by 69 publications

References 76 publications

Two faces of triel bonds in boron trihalide complexes

Two faces of triel bonds in boron trihalide complexes

π⋅⋅⋅H⁺⋅⋅⋅π Hydrogen Bonds and Their Lithium and Gold Analogues: MP2 and CASPT2 Calculations

Hexacoordinated Tetrel‐Bonded Complexes between TF₄ (T=Si, Ge, Sn, Pb) and NCH: Competition between σ‐ and π‐Holes

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Are Various σ‐Hole Bonds Steered by the Same Mechanisms?

Cited by 69 publications

References 76 publications

Two faces of triel bonds in boron trihalide complexes

Two faces of triel bonds in boron trihalide complexes

π⋅⋅⋅H+⋅⋅⋅π Hydrogen Bonds and Their Lithium and Gold Analogues: MP2 and CASPT2 Calculations

Hexacoordinated Tetrel‐Bonded Complexes between TF4 (T=Si, Ge, Sn, Pb) and NCH: Competition between σ‐ and π‐Holes

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π⋅⋅⋅H⁺⋅⋅⋅π Hydrogen Bonds and Their Lithium and Gold Analogues: MP2 and CASPT2 Calculations

Hexacoordinated Tetrel‐Bonded Complexes between TF₄ (T=Si, Ge, Sn, Pb) and NCH: Competition between σ‐ and π‐Holes