Experimental evidence for delocalization of the lone-pair orbital in methanamine from (e,2e) spectroscopy

1984 ◽  
Vol 106 (4) ◽  
pp. 976-979 ◽  
Author(s):  
J. A. Tossell ◽  
S. M. Lederman ◽  
J. H. Moore ◽  
M. A. Coplan ◽  
D. J. Chornay
Keyword(s):  
Experimental Evidence ◽  
Lone Pair ◽  
Lone Pair Orbital

ChemInform Abstract: EXPERIMENTAL EVIDENCE FOR DELOCALIZATION OF THE LONE-PAIR ORBITAL IN METHANAMINE FROM (E,2E) SPECTROSCOPY

1984 ◽  
Vol 15 (21) ◽  
Author(s):  
J. A. TOSSELL ◽  
S. M. LEDERMAN ◽  
J. H. MOORE ◽  
M. A. COPLAN ◽  
D. J. CHORNAY
Keyword(s):  
Experimental Evidence ◽  
Lone Pair ◽  
Lone Pair Orbital

Amino group stretching vibrations in primary aliphatic amines

1967 ◽  
Vol 45 (14) ◽  
pp. 1605-1610 ◽  
Author(s):  
P. J. Krueger ◽  
D. W. Smith
Keyword(s):  
Alkyl Chain ◽  
Inductive Effect ◽  
Lone Pair ◽  
Aliphatic Amines ◽  
Lone Pair Orbital ◽  
First Approximation ◽  
Symmetric Band ◽  
Integrated Intensity ◽  
Stretching Vibrations ◽  
Primary Aliphatic Amines

Primary aliphatic amines can be characterized by infrared spectroscopy as to the nature and degree of branching of the alkyl chain, using the fundamental antisymmetric and symmetric NH2 stretching frequencies measured in dilute C2Cl4 solution. Where steric and direct conjugation effects are absent both frequencies and the integrated intensity of the antisymmetric band increase linearly with decreasing inductive electron-donating power of the alkyl chain. The integrated intensity of the symmetric band, which is smaller than that for the antisymmetric band in all the 26 compounds studied, is independent of the inductive nature of the alkyl chain as a first approximation. These results indicate that the N-atom lone-pair orbital in RNH2 plays a negligibly small role in modifying the inductive effect of R on NH2 frequencies and intensities as long as the N-atom hybridization remains sp3.

scholarly journals A G2(MP2) theoretical study of substituent effects on H3BNHnCl3−n (n= 3-0) donor-acceptor complexes

2008 ◽  
Vol 6 (3) ◽  
pp. 400-403 ◽  
Author(s):  
Hafid Anane ◽  
Soufiane Houssame ◽  
Abdelali Guerraze ◽  
Abdeladim Guermoune ◽  
Abderrahim Boutalib ◽  
...  
Keyword(s):  
Theoretical Study ◽  
Substituent Effects ◽  
Lone Pair ◽  
Proton Affinities ◽  
Lone Pair Orbital ◽  
Chlorine Substitution ◽  
Donor Acceptor ◽  
Nitrogen Lone Pair ◽  
The Stability ◽  
N Compounds

AbstractThe complexation energies of H3BNHnCl3−n (n= 3-0) complexes and the proton affinities of NHnCl3−n compounds have been computed at the G2(MP2) level of theory. G2(MP2) results show that the successive chlorine substitution on the ammonia decreases both the basicity of the NHnCl3−n ligands and the stability of H3BNHnCl3−n complexes. The findings are interpreted in terms of the rehybridisation of the nitrogen lone-pair orbital. The NBO partitioning scheme shows that the variation of the N-H and N-Cl bond lengths, upon complexation, is due to variation of “s” character in these bonds.

Lone-Pair Orbital Interactions in Polythiaadamantanes

2006 ◽  
Vol 110 (32) ◽  
pp. 9887-9899 ◽  
Author(s):  
Joseph E. Norton ◽  
Alejandro L. Briseno ◽  
Fred Wudl ◽  
K. N. Houk
Keyword(s):  
Lone Pair ◽  
Orbital Interactions ◽  
Lone Pair Orbital

The Importance of Conformation of the Tetrahedral Intermediate in the Hydrolysis of Amides. Selective Cleavage of the Tetrahedral Intermediate Controlled by Orbital Orientation

1973 ◽  
Vol 51 (10) ◽  
pp. 1665-1669 ◽  
Author(s):  
Pierre Deslongchamps ◽  
Claude Lebreux ◽  
Roland Taillefer
Keyword(s):  
Experimental Evidence ◽  
Lone Pair ◽  
Tetrahedral Intermediate ◽  
Basic Hydrolysis ◽  
Hydrolysis Of ◽  
Orbital Orientation

The basic hydrolysis of N-disubstituted imidate salts proceeds via a hemi-orthoamide tetrahedral intermediate which can in principle give amide–alcohol or ester–amine products. Experimental evidence has been obtained which shows that the specific conformation of the tetrahedral intermediate determines products formation and it is further suggested that the orientation of the lone pair orbitals of the heteroatoms governs this remarkable selective decomposition.

scholarly journals Strong Tetrel Bonds: Theoretical Aspects and Experimental Evidence

Molecules ◽  
2018 ◽  
Vol 23 (10) ◽  
pp. 2642 ◽  
Author(s):  
Mehdi Esrafili ◽  
Parisasadat Mousavian
Keyword(s):  
Experimental Evidence ◽  
Noncovalent Interactions ◽  
Lone Pair ◽  
Lewis Base ◽  
Orbital Interaction ◽  
Bond Interaction ◽  
Tetrel Bond ◽  
Potential Applications ◽  
Bonding Properties ◽  
Bonded Complexes

In recent years, noncovalent interactions involving group-14 elements of the periodic table acting as a Lewis acid center (or tetrel-bonding interactions) have attracted considerable attention due to their potential applications in supramolecular chemistry, material science and so on. The aim of the present study is to characterize the geometry, strength and bonding properties of strong tetrel-bond interactions in some charge-assisted tetrel-bonded complexes. Ab initio calculations are performed, and the results are supported by the quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) approaches. The interaction energies of the anionic tetrel-bonded complexes formed between XF3M molecule (X=F, CN; M=Si, Ge and Sn) and A− anions (A−=F−, Cl−, Br−, CN−, NC− and N3−) vary between −16.35 and −96.30 kcal/mol. The M atom in these complexes is generally characterized by pentavalency, i.e., is hypervalent. Moreover, the QTAIM analysis confirms that the anionic tetrel-bonding interaction in these systems could be classified as a strong interaction with some covalent character. On the other hand, it is found that the tetrel-bond interactions in cationic tetrel-bonded [p-NH3(C6H4)MH3]+···Z and [p-NH3(C6F4)MH3]+···Z complexes (M=Si, Ge, Sn and Z=NH3, NH2CH3, NH2OH and NH2NH2) are characterized by a strong orbital interaction between the filled lone-pair orbital of the Lewis base and empty BD*M-C orbital of the Lewis base. The substitution of the F atoms in the benzene ring provides a strong orbital interaction, and hence improved tetrel-bond interaction. For all charge-assisted tetrel-bonded complexes, it is seen that the formation of tetrel-bond interaction is accompanied bysignificant electron density redistribution over the interacting subunits. Finally, we provide some experimental evidence for the existence of such charge-assisted tetrel-bond interactions in crystalline phase.

scholarly journals An Example of Lone Pair Orbital and Their Interaction——Gas Phase Ultravlolet Photoelctron Spectroscople Study of some Nitrogen Heterocyclle Compounds

1992 ◽  
Vol 8 (06) ◽  
pp. 809-813
Author(s):  
Wang Dian-Xun ◽  
◽  
Wang Dong ◽  
Zhao Heng-Qi ◽  
Tang Qing ◽  
...  
Keyword(s):  
Gas Phase ◽  
Lone Pair ◽  
Lone Pair Orbital
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