scholarly journals Lone pair⋯π interactions involving carbonyl π-systems: Experimental and theoretical study of the complexes of COF2 and COFCl with dimethyl ether

2016 ◽  
Vol 476 ◽  
pp. 1-8 ◽  
Author(s):  
Yannick Geboes ◽  
Frank De Proft ◽  
Wouter A. Herrebout
Keyword(s):  
Dimethyl Ether ◽  
Theoretical Study ◽  
Lone Pair ◽  
Π Interactions

scholarly journals Can lone pair-π and cation-π interactions coexist? A theoretical study

2011 ◽  
Vol 9 (1) ◽  
pp. 25-34 ◽  
Author(s):  
Carolina Estarellas ◽  
Antonio Frontera ◽  
David Quiñonero ◽  
Pere Deyà
Keyword(s):  
Interaction Potential ◽  
Theoretical Study ◽  
Noncovalent Interactions ◽  
Lone Pair ◽  
Geometric Features ◽  
Aromatic Rings ◽  
Partition Scheme ◽  
Π Interactions ◽  
Cooperativity Effects ◽  
Structural Database

AbstractThe interplay between two important noncovalent interactions involving different aromatic rings is studied by means of ab initio calculations (MP2/6-31++G**) computing the non-additivity energies. In this study we demonstrate the existence of cooperativity effects when cation-π and lone pair-π interactions coexist in the same system. These effects are studied theoretically using energetic and geometric features of the complexes. In addition we use Bader’s theory of atoms-in-molecules and Molecular Interaction Potential with polarization (MIPp) partition scheme to characterize the interactions. Experimental evidence for this combination of interactions has been obtained from the Cambridge Structural Database.

Energetic Effects between Halogen Bonds and Anion-π or Lone Pair-π Interactions: A Theoretical Study

2012 ◽  
Vol 116 (10) ◽  
pp. 2591-2597 ◽  
Author(s):  
Yunxiang Lu ◽  
Yingtao Liu ◽  
Haiying Li ◽  
Xiang Zhu ◽  
Honglai Liu ◽  
...  
Keyword(s):  
Theoretical Study ◽  
Lone Pair ◽  
Halogen Bonds ◽  
Π Interactions

Through-Space Transmission of 19F-13C Coupling Via an Intermediate Bond. An Experimental and Theoretical Study

1987 ◽  
Vol 40 (12) ◽  
pp. 1923 ◽  
Author(s):  
ID Rae ◽  
ID Rae ◽  
A Staffa ◽  
A Staffa ◽  
AC Diz ◽  
...  
Keyword(s):  
Theoretical Study ◽  
Lone Pair ◽  
Electron Excitation ◽  
Carbonyl Groups ◽  
Polarization Propagator ◽  
Close Proximity ◽  
Fermi Contact ◽  
Intramolecular Hydrogen ◽  
Intermediate Bond ◽  
Insight Into

In order to obtain a deeper insight into the title effect, several compounds with an F atom very close to a C-H of a nearby functional group were synthesized and the relevant couplings measured. The most conspicuous case was that of 8-fluoro-2-hydroxynaphthalene-1-carbaldehyde where a close proximity between the F and H atoms is the result of fluorine-oxygen repulsion and the formation of an intramolecular hydrogen bond between the hydroxyl and carbonyl groups. The experimental four-bond J(F,CHO) coupling is 26.2 Hz. A compound very similar to this one, but without the OH group, was chosen on which to perform a polarization propagator analysis of the through-space (TS) coupling pathways, at the RPA-INDO level. The expression for the TS coupling in terms of the projected polarization propagator and perturbators was numerically analysed. It is found that this coupling is completely dominated by a TS component of the Fermi contact (FC) term, the main features of which are: ( i ) It decays exponentially with the F-H distance; (ii) Its main contribution comes from an electron excitation involving the F lone-pair, the C-H bond of the CHO moiety and its corresponding antibonding orbital;(iii) The π-type lone-pair does not contribute to the TS coupling pathway of the FC term.

2-Pyridylcyanoxime-NiIIClusters with Unusual Topologies: Lone-Pair-π Interactions and Magnetic Properties

2014 ◽  
Vol 2014 (31) ◽  
pp. 5443-5450 ◽  
Author(s):  
Albert Escuer ◽  
Jordi Esteban ◽  
Júlia Mayans ◽  
Mercè Font-Bardia
Keyword(s):  
Magnetic Properties ◽  
Lone Pair ◽  
Π Interactions

scholarly journals Crystal structure of poly[[[μ4-5-(9H-carbazol-9-yl)isophthalato][μ3-5-(9H-carbazol-9-yl)isophthalato]bis(dimethylformamide)(methanol)dizinc] dimethylformamide monosolvate]

2015 ◽  
Vol 71 (8) ◽  
pp. m152-m153 ◽  
Author(s):  
Liubov M. Lifshits ◽  
Charles Campana ◽  
Jeremy K. Klosterman
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bond ◽  
Title Compound ◽  
Solvent Molecule ◽  
Lone Pair ◽  
Π Interactions ◽  
Carboxylate Groups ◽  
Medium Strength ◽  
Secondary Building Units ◽  
Coordination Spheres

The structure of the polymeric title compound, {[Zn2(C20H11NO4)2(C3H7NO)2(CH3OH)]·C3H7NO}n, comprises carbazolylisophthalate moieties connecting dimetallic tetracarboxylate zinc secondary building units (SBUs) parallel to [100] and [010], leading to a layer-like arrangement parallel to (001). Each SBU consists of two Zn atoms in slightly distorted tetrahedral and octahedral coordination environments [Zn...Zn = 3.5953 (6) Å]. Three carboxylate groups bridge the two Zn atoms in a μ2-O:O′ mode, whereas the fourth coordinates through a single carboxylate O atom (μ1-O). The O atoms of two dimethylformamide (DMF) and one methanol molecule complete the Zn coordination spheres. The methanol ligand interacts with the noncoordinating DMF moleculeviaan O—H...O hydrogen bond of medium strength. Carbazoles between the layers interdigitate through weak C—H....π interactions to form a laminar solid stacked along [010]. Two kinds of C—H...π interactions are present, both with a distance of 2.64 Å, between the H atoms and the centroids, and a third C—H...π interaction, where the aromatic H atom is located above the carbazole N-atom lone pair (H...N = 2.89 Å). Several C—H...O interactions occur between the coordinating DMF molecule, the DMF solvent molecule, and ligating carboxylate O atoms.

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