The potential of pnicogen bonding for catalysis – a computational study

2017 ◽  
Vol 15 (38) ◽  
pp. 8037-8045 ◽  
Author(s):  
J. Schmauck ◽  
M. Breugst
Keyword(s):  
Phosphorus Atom ◽  
Computational Study ◽  
Noncovalent Interaction ◽  
Lewis Base ◽  
Catalytic Reactions

Computational investigations reveal that pnicogen bonding, a noncovalent interaction between the electrophilic region of a phosphorus atom and a Lewis base, can activate electrophiles in catalytic reactions.

scholarly journals Lewis base character of the phosphorus atom in phosphanido-niobocene complexes. Synthesis of new early–early homo- and heterobimetallic entities

2011 ◽  
Vol 40 (11) ◽  
pp. 2622 ◽  
Author(s):  
R. Reguillo-Carmona ◽  
A. Antiñolo ◽  
S. García-Yuste ◽  
I. López-Solera ◽  
A. Otero
Keyword(s):  
Phosphorus Atom ◽  
Lewis Base ◽  
Early Homo

Hydrogenation of Olefins, Alkynes, Allenes, and Arenes by Borane-based Frustrated Lewis Pairs

Synthesis ◽  
2021 ◽  
Author(s):  
Felix Wech ◽  
Urs Gellrich
Keyword(s):  
Transition Metal ◽  
Hydride Transfer ◽  
Lewis Base ◽  
Catalytic Reactions ◽  
Transfer Reactions ◽  
Organic Substrates ◽  
Frustrated Lewis Pairs ◽  
Hydrogen Activation ◽  
Hydrogenation Catalysts ◽  
Lewis Pairs

In recent years, borane-based frustrated Lewis pairs proved to be efficient hydrogenation catalysts and became an alternative to transition metal-based systems. The hydrogen activation by classic FLPs leads to a protonated Lewis base and a borohydride. Consequently, hydrogenations catalyzed by classic FLPs consist of stepwise hydride transfer reactions and protonations (or vice versa). More recently, systems that operate via an initial hydroboration have allowed extending the substrate scope for FLP catalyzed hydrogenations. Within this review, hydrogenations of organic substrates catalyzed by borane-based frustrated Lewis pairs are discussed. Emphasis is given to the mechanistic aspects of these catalytic reactions.

scholarly journals Halogen-bonded adduct of 1,2-dibromo-1,1,2,2-tetrafluoroethane and 1,4-diazabicyclo[2.2.2]octane

2015 ◽  
Vol 71 (10) ◽  
pp. 900-902 ◽  
Author(s):  
Alan K. Brisdon ◽  
Abeer M. T. Muneer ◽  
Robin G. Pritchard
Keyword(s):  
Intermolecular Interaction ◽  
Halogen Atom ◽  
Halogen Bonding ◽  
Vapour Phase ◽  
Noncovalent Interaction ◽  
Lewis Base ◽  
Halogen Bonds ◽  
One Dimensional ◽  
Bonding Systems ◽  
Van Der Waals Radii

Halogen bonding is an intermolecular interaction capable of being used to direct extended structures. Typical halogen-bonding systems involve a noncovalent interaction between a Lewis base, such as an amine, as an acceptor and a halogen atom of a halofluorocarbon as a donor. Vapour-phase diffusion of 1,4-diazabicyclo[2.2.2]octane (DABCO) with 1,2-dibromotetrafluoroethane results in crystals of the 1:1 adduct, C2Br2F4·C6H12N2, which crystallizes as an infinite one-dimensional polymeric structure linked by intermolecular N...Br halogen bonds [2.829 (3) Å], which are 0.57 Å shorter than the sum of the van der Waals radii.

scholarly journals On the Bonding Situation in Stannocene and Plumbocene N-Heterocyclic Carbene Complexes

2019 ◽  
Author(s):  
Diego Andrada ◽  
Sergi Danés ◽  
Lisa Wirtz ◽  
Carsten Mueller ◽  
Volker Huch ◽  
...  
Keyword(s):  
Computational Study ◽  
Decomposition Analysis ◽  
Heterocyclic Carbenes ◽  
Lewis Base ◽  
Energy Decomposition Analysis ◽  
Dispersion Interactions ◽  
X Ray Diffraction ◽  
Group 14 ◽  
Carbene Complexes ◽  
Covalent Interactions

A detailed experimental and computational study of a series of stannocene and plumbocene N-heterocyclic carbene complexes is presented. This unique class of group 14 Lewis acid base adducts was obtained from reactions of the corresponding metallocenes and N-heterocyclic carbenes (NHC), and were structurally characterized by single crystal X-ray diffraction. The obtained structures show a perpendicular pose of the NHC with respect to the metallocene, hence precluding the maximal interaction between the moieties. The nature of the Sn-CNHC and Pb-CNHC bonds have been investigated by applying Energy Decomposition Analysis (EDA-NOCV). For the sake of comparison, known stannocene and plumbocene Lewis base complexes have been included in the series. The attractive chemical bonding interactions are around 50% electrostatic, 30% covalent and 20% dispersion. Indeed, dispersion interactions play a determining role the bigger the substituents become. The covalent interactions derive from the donation of the carbene ligand into the empty p orbital of the metallocene.

Exchange of Cl+ between Lone-Pair Donors and π-Donors: A Computational Study

2000 ◽  
Vol 6 (2) ◽  
pp. 153-160 ◽  
Author(s):  
Theis I. Sølling ◽  
Leo Radom
Keyword(s):  
Ab Initio ◽  
Computational Study ◽  
Lone Pair ◽  
Binding Energies ◽  
Lewis Base ◽  
Molecular Orbital Calculations ◽  
Reaction Energy ◽  
Lewis Bases ◽  
Donor Ability ◽  
Reaction Energies

The chemistry of mono-adducts ([Cl–X]+) between Cl+ and a Lewis base (X = NH3, H2O, HF, PH3, H2S or HCl) has been investigated using ab initio molecular orbital calculations at the G2 level. The reactions of such mono-adducts with additional Lewis bases (Y) are found to give [Y–Cl]+ plus X, generally without an intermediate barrier, via a bis-adduct [Y–Cl–X]+. The binding energies of the bis-adduct and the reaction energies are related to the donor properties of the Lewis bases. The reactions between the mono-adducts [Cl–X]+ and the π-donors ethylene and acetylene yield chloriranium and chlorirenium ions, respectively. These reactions proceed via complexes that resemble either the reactants or products depending on the sign of the reaction energy, the latter in turn being determined by the donor ability of the Lewis base. Results for the chlorine systems are compared with those for the corresponding phosphorus systems investigated previously.

scholarly journals Ab-initio computational study of noncovalent interaction between peptide and alkaline metal ions on HF/6-31 G** level

2018 ◽  
Author(s):  
Parsaoran Siahaan ◽  
Rinaldy Christian ◽  
Anisa Nur Fauziah ◽  
Dwi Hudiyanti ◽  
Vivitri Dewi Prasasty
Keyword(s):  
Metal Ions ◽  
Ab Initio ◽  
Computational Study ◽  
Noncovalent Interaction ◽  
Alkaline Metal
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