scholarly journals Carboranes as Lewis Acids: Tetrel Bonding in CB11H11 Carbonium Ylide

Crystals ◽  
2021 ◽  
Vol 11 (4) ◽  
pp. 391
Author(s):  
Maxime Ferrer ◽  
Ibon Alkorta ◽  
José Elguero ◽  
Josep M. Oliva-Enrich
Keyword(s):  
Lewis Acid ◽  
Lewis Acids ◽  
Molecular Electrostatic Potential ◽  
Weak Interactions ◽  
Topological Analysis ◽  
Closed Shell ◽  
Lewis Bases ◽  
High Level ◽  
Quantum Chemical Computations ◽  
Vacant Orbital

High-level quantum-chemical computations (G4MP2) are carried out in the study of complexes featuring tetrel bonding between the carbon atom in the carbenoid CB11H11—obtained by hydride removal in the C-H bond of the known closo-monocarbadodecaborate anion CB11H12(−) and acting as Lewis acid (LA)—and Lewis bases (LB) of different type; the electron donor groups in the tetrel bond feature carbon, nitrogen, oxygen, fluorine, silicon, phosphorus, sulfur, and chlorine atomic centres in neutral molecules as well as anions H(−), OH(−), and F(−). The empty radial 2pr vacant orbital on the carbon centre in CB11H11, which corresponds to the LUMO, acts as a Lewis acid or electron attractor, as shown by the molecular electrostatic potential (MEP) and electron localization function (ELF). The thermochemistry and topological analysis of the complexes {CB11H11:LB} are comprehensively analysed and classified according to shared or closed-shell interactions. ELF analysis shows that the tetrel C⋯X bond ranges from very polarised bonds, as in H11B11C:F(-) to very weak interactions as in H11B11C⋯FH and H11B11C⋯O=C=O.

scholarly journals Tetrel Bonding in CB11H11 Carbonium Ylide

2021 ◽  
Author(s):  
Maxime Ferrer ◽  
Ibon Alkorta ◽  
José Elguero ◽  
Josep M. Oliva-Enrich
Keyword(s):  
Lewis Acid ◽  
Quantum Chemical ◽  
Molecular Electrostatic Potential ◽  
Weak Interactions ◽  
Topological Analysis ◽  
Closed Shell ◽  
Lewis Bases ◽  
High Level ◽  
Quantum Chemical Computations ◽  
Vacant Orbital

High-level quantum-chemical computations (G4MP2) are carried out in the study of complexes featuring tetrel bonding between the carbon atom in the carbenoid CB11H11 - obtained by hydride removal in the C-H bond of the known closo-monocarbadodecaborate anion CB11H12() and acting as Lewis acid (LA) - and Lewis bases (LB) of different type; the electron donor groups in the tetrel bond feature carbon, nitrogen, oxygen, fluorine, silicon, phosphorus, sulphur and chlorine atomic centers in neutral molecules as well as anions H(-), OH(-) and F(-). The empty radial 2pr vacant orbital on the carbon center in CB11H11 , which corresponds to the LUMO, acts as a Lewis acid or electron attractor, as shown by the molecular electrostatic potential (MEP) and electron localization funcion (ELF). The thermochemistry and topological analysis of the complexes {CB11H11:LB} are comprehensively analyzed, and classified according to sharing or closed-shell interactions. ELF analysis shows that the tetrel C···X bond ranges from very polarised bonds, as in H11B11C:F() to very weak interactions as in H11B11C···FH and H11B11C···O=C=O.

Lewis Acid – Base Interactions Between Bis-π-cyclopentadienyl Tungsten and Molybdenum Dihydrides, Cp2MH2, and some Main Group III Moieties

1971 ◽  
Vol 49 (15) ◽  
pp. 2504-2507 ◽  
Author(s):  
A. Storr ◽  
B. S. Thomas
Keyword(s):  
Lewis Acid ◽  
Lewis Acids ◽  
Benzene Solution ◽  
Main Group ◽  
Acid Base ◽  
Group Iii ◽  
Lewis Bases

Combination of the Lewis bases Cp2MH2 (where M = W or Mo) with the Group III Lewis acids AlR3 (where R = Me, Et, or Ph) and AlMe2H has yielded a series of 1:1 complexes of the type Cp2MH2•AlR3. A number of the complexes undergoes a slow elimination of hydrogen or alkane in benzene solution. Attempts to isolate mixed hydride adducts of the type, Cp2MH2•M′H3 (where M′ = Al or Ga), were unsuccessful.

Lewis acid addticts of α,β-unsaturated carbonyl and nitrile compounds. A calorimetric study

1982 ◽  
Vol 60 (6) ◽  
pp. 809-812 ◽  
Author(s):  
Ronald F. Childs ◽  
D. Lindsay Mulholland ◽  
Alan Nixon
Keyword(s):  
Lewis Acid ◽  
Qualitative Agreement ◽  
Lewis Acids ◽  
Mesityl Oxide ◽  
Poor Correlation ◽  
Calorimetric Study ◽  
Lewis Bases ◽  
Quantitative Correlation

Enthalpies of complexation of the α,β-unsaturated Lewis bases crotonaldehyde, 1; methyl crotonate, 2; mesityl oxide, 3; and crotononitrile, 4; with each of the Lewis acids SnCl4, TiCl4, SbCl5, and BCl3 were measured in solution in CH2Cl2. The results indicate that while a qualitative agreement exists in the ranking of Lewis acids for each of the Lewis bases, there is only a modest quantitative correlation. Similarly, when compared with an nmr-derived Lewis acid scale, the enthalpies were found to agree with the qualitative ranking of Lewis acids, but exhibited only a poor correlation.

Spontaneous bond dissociation cascades induced by Ben clusters (n = 2,4)

2021 ◽  
Author(s):  
Eva Vos ◽  
Inés Corral ◽  
M. Merced Montero-Campillo ◽  
Otilia Mó ◽  
José Elguero ◽  
...  
Keyword(s):  
Lewis Acids ◽  
Lewis Bases ◽  
Bond Dissociation ◽  
Multireference Methods

Be4 clusters are very powerful Lewis acids leading to the total dissociation of all the bonds of the Lewis bases interacting with them. The product of the bond dissociation cascade possesses a hyper-coordinated center. Multireference methods are needed to correctly describe these complexes.

Lewis Acid-Promoted Suzuki Reaction using Palladium Chloride Anchored on a Polymer as a Catalyst

2008 ◽  
Vol 61 (8) ◽  
pp. 610 ◽  
Author(s):  
Guozhi Fan ◽  
Hanjun Zhang ◽  
Siqing Cheng ◽  
Zhandong Ren ◽  
Zhijun Hu ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Lewis Acid ◽  
Lewis Acids ◽  
Heterogeneous Catalysts ◽  
Suzuki Reaction ◽  
Cross Coupling ◽  
Palladium Chloride ◽  
Coupling Reactions ◽  
Cross Coupling Reactions ◽  
Recoverable Catalyst

Palladium chloride anchored on polystyrene modified by 5-amino-1,10-phenanthroline was prepared and used as an efficient recoverable catalyst for Suzuki cross-coupling reactions. The heterogeneous catalysts can be easily separated from the reaction mixture and reused for five cycles without significant Pd leaching and loss of catalytic activity. Rate enhancement in the Suzuki reaction by Lewis acids was also studied.

Synthesis of pyrrolo[1,2-a]naphthyridines by Lewis acid mediated cycloisomerization

2017 ◽  
Vol 15 (15) ◽  
pp. 3216-3231 ◽  
Author(s):  
Anika Flader ◽  
Silvio Parpart ◽  
Peter Ehlers ◽  
Peter Langer
Keyword(s):  
Lewis Acid ◽  
Lewis Acids

Functionalized pyrrolo[1,2-a]naphthyridines were synthesized by application of PtCl2 and Bi(OTf)3 as simple Lewis acids in a cycloisomerization reaction.

Building new discrete supramolecular assemblies through the interaction of iso-tellurazole N-oxides with Lewis acids and bases

2017 ◽  
Vol 203 ◽  
pp. 187-199 ◽  
Author(s):  
Peter C. Ho ◽  
Hilary A. Jenkins ◽  
James F. Britten ◽  
Ignacio Vargas-Baca
Keyword(s):  
Electron Acceptor ◽  
Lewis Acids ◽  
Heterocyclic Carbenes ◽  
Supramolecular Assemblies ◽  
Triphenyl Phosphine ◽  
Tellurium Atom ◽  
Lewis Bases ◽  
Acids And Bases ◽  
Lewis Acids And Bases

The supramolecular macrocycles spontaneously assembled by iso-tellurazole N-oxides are stable towards Lewis bases as strong as N-heterocyclic carbenes (NHC) but readily react with Lewis acids such as BR3 (R = Ph, F). The electron acceptor ability of the tellurium atom is greatly enhanced in the resulting O-bonded adducts, which consequently enables binding to a variety of Lewis bases that includes acetonitrile, 4-dimethylaminopyridine, 4,4′-bipyridine, triphenyl phosphine, a N-heterocyclic carbene and a second molecule of iso-tellurazole N-oxide.

Pyridinediimine Iron Dicarbonyl Complexes with Pendant Lewis Bases and Lewis Acids Located in the Secondary Coordination Sphere

2013 ◽  
Vol 2013 (22-23) ◽  
pp. 4008-4015 ◽  
Author(s):  
Zachary Thammavongsy ◽  
Micah E. LeDoux ◽  
Andrew G. Breuhaus-Alvarez ◽  
Takele Seda ◽  
Lev N. Zakharov ◽  
...  
Keyword(s):  
Coordination Sphere ◽  
Lewis Acids ◽  
Lewis Bases ◽  
Secondary Coordination Sphere

The role of the Lewis acid−base properties in the supramolecular association of 1,2,5-chalcogenadiazoles

2013 ◽  
Vol 91 (5) ◽  
pp. 338-347 ◽  
Author(s):  
Anthony F. Cozzolino ◽  
Philip J.W. Elder ◽  
Lucia Myongwon Lee ◽  
Ignacio Vargas-Baca
Keyword(s):  
Topological Analysis ◽  
Structural Features ◽  
Lewis Acidity ◽  
Electron Localization ◽  
Dispersion Forces ◽  
Acid Base ◽  
Lewis Bases ◽  
The Individual ◽  
Secondary Bonding

The secondary bonding interactions that link the supramolecular structures assembled by 1,2,5-chalcogenadiazoles were analyzed through explicit orthogonalization of molecular orbitals (NBO), topological analysis of the electron density (AIM), and the electron localization function (ELF). The results of these analyses are consistent with a bonding description that attributes important covalent and electrostatic character to these interactions. Application of these analyses to the individual molecules highlighted the structural features from which each of those contributions originates, namely the polarity and modest strength of the E–N bond. Both of these effects increase along the series S, Se, Te. Perturbations to the heterocycle electronic structure that result in a weaker and more polar E–N bond cause an increase in the Lewis acidity at the chalcogen centre, which in turn leads to stronger secondary bonding interactions with Lewis bases. Additionally, the contribution of dispersion forces is not negligible and is most important in the case of sulfur.

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