Intramolecular Hydrogen Bond Activation of Aza-Methylene Imines in Hydrogen Bond Bifunctional Catalysis - A Density Functional Theory Study

2018 ◽  
Vol 2019 (2-3) ◽  
pp. 574-581 ◽  
Author(s):  
Ana Martín-Sómer ◽  
Enrique M. Arpa ◽  
Sergio Díaz-Tendero ◽  
José Alemán
Keyword(s):  
Density Functional Theory ◽  
Hydrogen Bond ◽  
Intramolecular Hydrogen Bond ◽  
Density Functional ◽  
Bond Activation ◽  
Bifunctional Catalysis ◽  
Density Functional Theory Study ◽  
Functional Theory ◽  
Intramolecular Hydrogen

An X-ray crystallographic and density functional theory study of (3Z)-4-(5-ethylsulfonyl-2-hydroxyanilino)pent-3-en-2-one and (3Z)-4-(5-tert-butyl-2-hydroxyanilino)pent-3-en-2-one

2013 ◽  
Vol 69 (3) ◽  
pp. 258-262
Author(s):  
Kate J. Akerman ◽  
Orde Q. Munro
Keyword(s):  
Density Functional Theory ◽  
Hydrogen Bond ◽  
Intramolecular Hydrogen Bond ◽  
Density Functional ◽  
Intermolecular Hydrogen Bond ◽  
Functional Theory ◽  
One Dimensional ◽  
X Ray ◽  
Intramolecular Hydrogen ◽  
Hydrogen Bonded

The Schiff base enaminones (3Z)-4-(5-ethylsulfonyl-2-hydroxyanilino)pent-3-en-2-one, C13H17NO4S, (I), and (3Z)-4-(5-tert-butyl-2-hydroxyanilino)pent-3-en-2-one, C15H21NO2, (II), were studied by X-ray crystallography and density functional theory (DFT). Although the keto tautomer of these compounds is dominant, the O=C—C=C—N bond lengths are consistent with some electron delocalization and partial enol character. Both (I) and (II) are nonplanar, with the amino–phenol group canted relative to the rest of the molecule; the twist about the N(enamine)—C(aryl) bond leads to dihedral angles of 40.5 (2) and −116.7 (1)° for (I) and (II), respectively. Compound (I) has a bifurcated intramolecular hydrogen bond between the N—H group and the flanking carbonyl and hydroxy O atoms, as well as an intermolecular hydrogen bond, leading to an infinite one-dimensional hydrogen-bonded chain. Compound (II) has one intramolecular hydrogen bond and one intermolecular C=O...H—O hydrogen bond, and consequently also forms a one-dimensional hydrogen-bonded chain. The DFT-calculated structures [in vacuo, B3LYP/6-311G(d,p) level] for the keto tautomers compare favourably with the X-ray crystal structures of (I) and (II), confirming the dominance of the keto tautomer. The simulations indicate that the keto tautomers are 20.55 and 18.86 kJ mol−1lower in energy than the enol tautomers for (I) and (II), respectively.

Does a multiply bonded oxo ligand directly participate in B–H bond activation by a high-valent di-oxo-molybdenum(vi) complex? A density functional theory study

2015 ◽  
Vol 5 (6) ◽  
pp. 3259-3269 ◽  
Author(s):  
Liangfang Huang ◽  
Jiandi Wang ◽  
Xiaoqin Wei ◽  
Haiyan Wei
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Bond Activation ◽  
Organic Substrates ◽  
Density Functional Theory Study ◽  
Molybdenum Complex ◽  
Functional Theory ◽  
Multiply Bonded ◽  
High Valent ◽  
Oxo Ligand

The multiply bonded oxo ligand does not participate in the activation of the B–H bond with organic substrates of amides, amines, and nitriles by the high-valent oxo-molybdenum complex MoO2Cl2.

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