An arene-stabilized η5-pentamethylcyclopentadienyl antimony dication acts as a source of Sb+ or Sb3+ cations

2020 ◽  
Vol 56 (85) ◽  
pp. 12953-12956
Author(s):  
Jiliang Zhou ◽  
Hyehwang Kim ◽  
Liu Leo Liu ◽  
Levy L. Cao ◽  
Douglas W. Stephan
Keyword(s):  
Lewis Acidity ◽  
Lewis Bases ◽  
Strong Lewis Acidity

The dicationic compound [(η5-Cp*)Sb(tol)][B(C6F5)4]2 (1) (tol = toluene), which exhibits strong Lewis acidity, reacts with Lewis bases to provide Sb+ or Sb3+ cations.

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.

Metallocenylborane, IV. Diborylverbindungen des Ferrocens und Cymantrens.

1976 ◽  
Vol 31 (8) ◽  
pp. 1028-1034 ◽  
Author(s):  
Werner Ruf ◽  
Thomas Renk ◽  
Walter Siebert
Keyword(s):  
Redox Reaction ◽  
Lewis Acidity ◽  
Lewis Bases ◽  
Nmr Data ◽  
Halogen Exchange ◽  
Donor Acceptor ◽  
C Nmr

Ferrocene reacts with BI3 and BBr3 to give 1,1′-bis(dihalogenboryl)ferrocenes; the cyclopentadienylring in cymantrene is twice borylated by BI3. By halogen exchange with AsF3 and AsCl3, by methylation with Sn(CH3)4, by cleavage of (C2H5)2O, by redox reaction with (CH3S)2 and by reaction with (C2H5)2NH the corresponding diborylferrocenes are obtained. The air-sensitive halogenborylferrocenes form donor-acceptor compounds with Lewis bases. 1H, 11B and 13C NMR data reflect increasing π-acceptor properties with increasing Lewis acidity of the boryl groups.

Thermodynamics of metal-ligand bond formation. XXIII. Lewis acidity of mercury(II) thiocyanate

1976 ◽  
Vol 29 (11) ◽  
pp. 2405 ◽  
Author(s):  
Y Farhangi ◽  
DP Graddon
Keyword(s):  
Bond Formation ◽  
Formation Constants ◽  
Adduct Formation ◽  
Lewis Acidity ◽  
Acetonitrile Solution ◽  
Enthalpies Of Formation ◽  
Dilute Solution ◽  
Lewis Bases ◽  
Metal Ligand ◽  
Ligand Bond

Thermodynamic data are reported for the reaction of Lewis bases with mercury(11) thiocyanate in acetonitrile solution. Pyridine, 4-methylpyridine and tetrahydrothiophen form 1 : 1 adducts with adduct formation constants and enthalpies of formation comparable to those with mercury(11) iodide. 1,l0-Phenanthroline, 2,2'-bipyridine and N,N,N',N?-tetramethylethane-1,2-diamine form chelate 1 : 1 adducts, but with enthalpies of formation little larger than that with pyridine. The phosphines, PPh3 and Pbu3, form 1 : 1 and 1 : 2 adducts of much greater stability, though the enthalpies of formation of these adducts are also similar to that with pyridine; Hg(SCN)2PBu3 is dimeric in dilute solution.

Lewis Acidity Scale of Diaryliodonium Ions toward Oxygen, Nitrogen, and Halogen Lewis Bases

2020 ◽  
Vol 142 (11) ◽  
pp. 5221-5233 ◽  
Author(s):  
Robert J. Mayer ◽  
Armin R. Ofial ◽  
Herbert Mayr ◽  
Claude Y. Legault
Keyword(s):  
Lewis Acidity ◽  
Lewis Bases ◽  
Acidity Scale

DFT Studies Provide Mechanistic Insight into Nickel-Catalyzed Cross-Coupling Involving Organoaluminum-Mediated C–O Bond Cleavage

Synlett ◽  
2017 ◽  
Vol 28 (19) ◽  
pp. 2565-2568 ◽  
Author(s):  
Chao Wang ◽  
Masanobu Uchiyama ◽  
Ze-Kun Yang
Keyword(s):  
Density Functional ◽  
Reaction Pathway ◽  
Bond Cleavage ◽  
Cross Coupling ◽  
Reductive Elimination ◽  
Lewis Acidity ◽  
Functional Theory ◽  
Mechanistic Insight ◽  
Insight Into ◽  
Strong Lewis Acidity

Density functional theory (DFT) calculations were performed to examine the reaction pathway of Ni-catalyzed cross-coupling with organoaluminum through C–O bond cleavage. The results indicate that the strong Lewis acidity of organoaluminums significantly facilitates the transmetalation step, but not the oxidative addition or reductive elimination step.

scholarly journals The Synthesis Properties and Reactivity of Lewis Acidic Aminoboranes

2021 ◽  
Author(s):  
Jordan N. Bentley ◽  
Selvyn A. Simoes ◽  
Ekadashi Pradhan ◽  
Tao Zeng ◽  
Chris Caputo
Keyword(s):  
Quantum Chemical ◽  
Lewis Acidity ◽  
Lewis Bases ◽  
Effective Catalyst ◽  
Frustrated Lewis Pair ◽  
Synthesis Properties ◽  
Significant Research

<div> <p>The evolution of frustrated Lewis pair chemistry has led to significant research into the development of new Lewis acidic boranes. Much of this has focused on modifying aryl substituents rather than introducing heteroatoms bound to boron. We recently reported unique Lewis acidic behaviour from bis(pentafluorophenyl)phenothiazylborane (<b>1</b>) for the heterolytic dehydrocoupling of stannanes. In this work, we synthesize and characterize a family of Lewis acidic aminoboranes and explored their reactivity with various Lewis bases as well as their efficacy as catalysts for stannane dehydrocoupling and hydrosilylation. Quantum chemical caluclations were undertaken to understand the origins of the Lewis acidity and the most Lewis acidic aminoborane (<b>5</b>) was found to be an effective catalyst even in coordinating solvents such as water or acetonitrile, suggesting the amino substituent provides a level of protection against competing donors. </p> </div> <br>

Binding of fullerenes to cadmium sulfide and cadmium selenide surfaces, photoluminescence as a probe of strong, Lewis acidity-driven, surface adduct formation

1993 ◽  
Vol 115 (17) ◽  
pp. 7789-7793 ◽  
Author(s):  
John Zhongju Zhang ◽  
Margret J. Geselbracht ◽  
Arthur B. Ellis
Keyword(s):  
Cadmium Sulfide ◽  
Cadmium Selenide ◽  
Adduct Formation ◽  
Lewis Acidity ◽  
Strong Lewis Acidity

Mechanistic insight to acidity effects of Ga/HZSM-5 on its activity for propane aromatization

RSC Advances ◽  
2015 ◽  
Vol 5 (112) ◽  
pp. 92222-92233 ◽  
Author(s):  
He Xiao ◽  
Junfeng Zhang ◽  
Peng Wang ◽  
Zhenzhou Zhang ◽  
Qingde Zhang ◽  
...  
Keyword(s):  
Synergistic Effect ◽  
Lewis Acidity ◽  
Brønsted Acidity ◽  
Brönsted Acidity ◽  
Mechanistic Insight ◽  
Propane Aromatization ◽  
Strong Lewis Acidity

Mechanistic insight to the synergistic effect between Brønsted acidity and strong Lewis acidity of Ga/HZSM-5 on propane aromatization activity.

Ketone coordination chemistry of the diborane t-BuCH=C[B(C6F5)2]2

1998 ◽  
Vol 76 (9) ◽  
pp. 1249-1255 ◽  
Author(s):  
Katrin Köhler ◽  
Warren E Piers
Keyword(s):  
Coordination Chemistry ◽  
Nmr Spectroscopy ◽  
Low Temperature ◽  
Temperature Dependence ◽  
Key Words ◽  
Lewis Acidity ◽  
High Yield ◽  
Lewis Bases ◽  
Equilibrium Yield ◽  
Boron Center

Reactions of the bifunctional borane t-BuCH=C[B(C6F5)2]2, 1, with simple Lewis bases were investigated to probe its Lewis acidity. Ethereal bases (Et2O, THF) bind very weakly, if at all, as no adducts were detectable in solution. Certain ketones, however, were observed to bind to 1. Acetone forms an adduct, 2, reversibly in solution (Keq at 293 K = 69.1), and the temperature dependence of this equilibrium yield thermodynamic parameters of H° = -59.5 ± 2.0 kJ mol-1; S° = -167 ± 4 J K-1 mol-1. Low temperature NMR spectroscopy suggests that the acetone binds to the more sterically accessible boron center trans to the t-Bu group. Ketone binding is strengthened when 2,3-diphenylcyclopropenone is reacted with 1, irreversibly forming an isolable adduct, 4, in high yield (95%). The availability of a resonance form incorporating the aromatic cyclopropenyl cation contributes to the added stability of this adduct in comparison to 2.Key words: organoboranes, diboranes, ketone complexes.

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