Gas phase Lewis acidity and basicity scales for boranes, phosphines and amines based on the formation of donor–acceptor complexes

2013 ◽  
Vol 1011 ◽  
pp. 44-56 ◽  
Author(s):  
Mariano Méndez ◽  
Andrés Cedillo
Keyword(s):  
Gas Phase ◽  
Lewis Acidity ◽  
Donor Acceptor ◽  
Acidity And Basicity

scholarly journals Controlling surface chemistry and mechanical properties of metal ionogels through Lewis acidity and basicity

2021 ◽  
Vol 9 (8) ◽  
pp. 4679-4686
Author(s):  
Coby J. Clarke ◽  
Richard P. Matthews ◽  
Alex P. S. Brogan ◽  
Jason P. Hallett
Keyword(s):  
Mechanical Properties ◽  
Ionic Liquids ◽  
Ethylene Glycol ◽  
Surface Chemistry ◽  
Lewis Acidity ◽  
Metal Species ◽  
Poly Ethylene Glycol ◽  
Acidity And Basicity ◽  
Poly Ethylene

Gels prepared from metal containing ionic liquids with cross-linked poly(ethylene glycol) have surface compositions and mechanical properties that can be controlled by Lewis basicity and acidity of the metal species.

scholarly journals Tuning of Hyperpolarizability, One- and Two-Photon Absorption of D-A and D-A-A Type Intramolecular Charge Transfer Based Sensors

2019 ◽  
Author(s):  
Pralok K. Samanta ◽  
Md Mehboob Alam ◽  
Ramprasad Misra ◽  
Swapan K. Pati
Keyword(s):  
Charge Transfer ◽  
Gas Phase ◽  
Density Functional ◽  
Intramolecular Charge Transfer ◽  
Photon Absorption ◽  
First Hyperpolarizability ◽  
Two Photon Absorption ◽  
Two Photon ◽  
Nlo Response ◽  
Donor Acceptor

Solvents play an important role in shaping the intramolecular charge transfer (ICT) properties of π-conjugated molecules, which in turn can affect their one-photon absorption (OPA) and two-photon absorption (TPA) as well as the static (hyper)polarizabilities. Here, we study the effect of solvent and donor-acceptor arrangement on linear and nonlinear optical (NLO) response properties of two novel ICT-based fluorescent sensors, one consisting of hemicyanine and dimethylaniline as electron withdrawing and donating groups (molecule 1), respectively and its boron-dipyrromethene (BODIPY, molecule 2)-fused counterpart (molecule 3). Density functional theoretical (DFT) calculations using long-range corrected CAM-B3LYP and M06-2X functionals, suitable for studying properties of ICT molecules, are employed to calculate the desired properties. The dipole moment (µ) as well as the total first hyperpolarizability (β<sub>total</sub>) of the studied molecules in the gas phase is dominantly dictated by the component in the direction of charge transfer. The ratios of vector component of first hyperpolarizability (β<sub>vec</sub>) to β<sub>total</sub> also reveal unidirectional charge transfer process. The properties of the medium significantly affect the OPA, hyperpolarizability and TPA properties of the studied molecules. Time dependent DFT (TDDFT) calculations suggest interchanging between two lowest excited states of molecule 3 from the gas phase to salvation. The direction of charge polarization and dominant transitions among molecular orbitals involved in the OPA and TPA processes are studied. The results presented are expected to be useful in tuning the NLO response of many ICT-based chromophores, especially those with BODIPY acceptors.<br>

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.

Trifluoromethylated Compounds with SiNN and SiON Backbone, and the Crystal Structures of Trimethyl- and Trichloro(trifluoromethyl)silane

2009 ◽  
Vol 64 (1) ◽  
pp. 83-92 ◽  
Author(s):  
Markus Woski ◽  
Norbert W. Mitzel
Keyword(s):  
Gas Phase ◽  
Solution Nmr ◽  
X Ray Diffraction ◽  
Experimental Ir ◽  
In Situ Techniques ◽  
Quantum Chemical Methods ◽  
Conformational Preferences ◽  
Donor Acceptor ◽  
Solid State Structures

The reaction of (F3C)Cl2SiCl3 with the lithiated hydrazine LiN(Me)NMe2 gives the compound (F3C)Cl2SiN(Me)NMe2 (1) and in traces Cl3SiN(Me)NMe2 (2). The reactions with LiN(SiMe3)NMe2 and LiONMe2 give (F3C)Cl2SiN(SiMe3)NMe2 (4) and (F3C)Cl2SiONMe2 (5), respectively. The compounds were characterised by multinuclear solution NMR, gas-phase IR spectroscopy and mass spectrometry. Information about conformational preferences of 1 and 4 can be extracted by comparing experimental IR spectra with those calculated by quantum chemical methods (B3LYP/6-311G**). The former show the gas phase of the β -donor-acceptor silanes 1 and 4 to be dominated by the anti conformations, while the calculations show a preference for the gauche conformers. The crystal structure of Cl3SiN(Me)NMe2 (2) has been determined. The solid-state structures of the Ruppert reagent F3C-SiMe3 (1) and its chlorine analogue F3C-SiCl3 (2) have also been determined by X-ray diffraction of single crystals grown by in situ techniques.

Acidity and basicity of thiocarboxamides in the gas phase

1994 ◽  
Vol 7 (9) ◽  
pp. 511-517 ◽  
Author(s):  
Mich�le Decouzon ◽  
Otto Exner ◽  
Jean-fran�ois Gal ◽  
Pierre-Charles Maria ◽  
Karel Waisser
Keyword(s):  
Gas Phase ◽  
Acidity And Basicity

Enhancement of Thermodynamic Gas-Phase Acidity and Basicity of Water by Means of Secondary Interactions

ChemPhysChem ◽  
2018 ◽  
Vol 19 (19) ◽  
pp. 2486-2491 ◽  
Author(s):  
M. Merced Montero-Campillo ◽  
Ibon Alkorta ◽  
José Elguero
Keyword(s):  
Gas Phase ◽  
Gas Phase Acidity ◽  
Secondary Interactions ◽  
Acidity And Basicity

scholarly journals Lewis Acidity and Basicity of Mixed Chlorometallate Ionic Liquids: Investigations from Surface Analysis and Fukui Function

Molecules ◽  
2018 ◽  
Vol 23 (10) ◽  
pp. 2516 ◽  
Author(s):  
Ying Liu ◽  
Juanfang Wang
Keyword(s):  
Ionic Liquids ◽  
Fukui Function ◽  
Lewis Acidity ◽  
Surface Ionization ◽  
Local Surface ◽  
Dual Descriptor ◽  
Mixed Metal ◽  
Estimated Parameters ◽  
Acidity And Basicity ◽  
Metal Anions

Mixed chlorometallate ionic liquids (ILs) have been regarded as potential solvents, catalysts, and reagents for many organic processes. The acidity and basicity of these ILs were correlated with theoretically estimated parameters such as electrostatic surface potential maxima and minima, average local surface ionization energy, and Fukui and dual descriptor functions. The introduction of metal chloride into the anions would influence the acidity/basicity of ILs by withdrawing the electron density from the cationic counterpart. For the [C4mim]-based ILs with the mixed-metal anions, the acidity tends to attenuate while the basicity becomes stronger, as compared to the corresponding chloroaluminate ILs. However, the acidity of [(C2H5)3NH]-based ILs with the mixed-metal anions are greater than that of the net chloroaluminate ILs. The Fukui function values showed that most of the mixed chlorometallate ILs belong to bifunctional distribution. The mixed chlorometallate ILs both have electrophilic and nucleophilic sites, which would be beneficial for their applications.

Design considerations for chiral frustrated Lewis pairs: B/N FLPs derived from 3,5-bicyclic aryl piperidines

2019 ◽  
Vol 48 (1) ◽  
pp. 133-141 ◽  
Author(s):  
Jolie Lam ◽  
Susanna Sampaolesi ◽  
James H. W. LaFortune ◽  
Jotham W. Coe ◽  
Douglas W. Stephan
Keyword(s):  
Computational Methods ◽  
Lewis Acidity ◽  
Frustrated Lewis Pairs ◽  
Design Considerations ◽  
Acidity And Basicity ◽  
Lewis Pairs

3,5-Bicyclic aryl piperidines are derivatized to generate chiral B/N FLPs. The Lewis acidities were assessed by experimental and computational methods. The activity in HD scrambling and hydrogenation was also assessed. These data demonstrate that a threshold of combined Lewis acidity and basicity is essential to activate H2.

The fluoroformate ion, FCO2−. An ion cyclotron resonance study of the gas phase Lewis acidity of carbon dioxide and related isoelectronic species

1978 ◽  
Vol 56 (8) ◽  
pp. 1069-1074 ◽  
Author(s):  
Terrance Brian McMahon ◽  
Colleen Joan Northcott
Keyword(s):  
Carbon Dioxide ◽  
Gas Phase ◽  
Lewis Acidity ◽  
Ion Cyclotron Resonance ◽  
Dissociation Energies ◽  
Ion Molecule Reactions ◽  
Gas Phase Acidity ◽  
Gas Phase Ion ◽  
Carbonyl Fluoride

The gas phase ion molecule reactions of a number of potential fluoride donors with carbon dioxide and carbonyl fluoride have been studied. By determination of preferential directions of fluoride transfer the fluoride affinities of carbon dioxide and carbonyl fluoride have been bracketed and found to be 33 ± 3 kcal/mol and 35 + 3 kcal/mol respectively. In addition, from gas phase acidity studies of acetyl fluoride and 2-fluoropropene the fluoride affinities of ketene and allene have been calculated to be 38 ± 2 kcal/mol and 15 ± 2 kcal/mol respectively. The order of fluoride affinities (Lewis acidities) of carbon dioxide, ketene, and allene have been examined and explained in terms of the electron affinities of the F—C(A)(B) species (A,B=O,CH2) and the C—F bond dissociation energies. These quantities have been estimated and the latter interpreted on the basis of the π bond energies of the three compounds.

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