A theoretical investigation of the isomers of diazomethane (CH2N2). I. Geometry, bonding, and chemical reactivity

1973 ◽  
Vol 26 (3) ◽  
pp. 461 ◽  
Author(s):  
BT Hart
Keyword(s):  
Electronic Structure ◽  
Theoretical Investigation ◽  
Electrostatic Potential ◽  
Chemical Reactivity ◽  
Structural Isomers

A searching theoretical investigation has been carried out on the five structural isomers of diazomethane, CH2N2; the isomers are diazomethane, cyanamide, isocyanamide, nitrilimine, and carbodiimide. The non- empirically calculated structures for the latter three compounds are the first to be reported. ��� Use has been made of localized exclusive orbitals to help explain the bonding and electronic structure in this series of molecules. ��� In addition, interesting use has been made of electrostatic potential maps in assessing positions of high nucleophilicity in each isomer. This information has allowed mechanistic pathways to be postulated for the protonation of diazomethane and cyanamide and for the production of isocyanamide from diazomethane.

Ring fusion isomers of dithienoborepins: perturbations of electronic structure, aromaticity, and reactivity in boron-containing polycyclic heteroaromatics

2017 ◽  
Vol 95 (4) ◽  
pp. 381-389 ◽  
Author(s):  
David R. Levine ◽  
Reid E. Messersmith ◽  
Maxime A. Siegler ◽  
John D. Tovar
Keyword(s):  
Electronic Structure ◽  
Computational Methods ◽  
Electronic Property ◽  
Rational Design ◽  
Chemical Reactivity ◽  
Molecular Property ◽  
Polycyclic Aromatics ◽  
Structural Isomers ◽  
Ring Fusion

Through a combination of rational design and synthetic serendipity, two new structural isomers of the dithienoborepin (DTB) architecture have been realized. Unlike previous members of this family, these boron-containing polycyclic aromatics are unsymmetrical with respect to the fusion orientation of the central borepin and flanking thiophene rings. Characterization of the unsymmetrical dithienoborepins through spectroscopic, crystallographic, electrochemical, and computational methods reveal that the electronics, aromaticity, and chemical reactivity can differ subtly (as for DTB 3) or in dramatic fashion (DTB 4) throughout the series, as dictated by the nature of the unique π-conjugation in each structure. Synthetic elaboration of the three most closely related DTB isomers (1, 2, and 3) into π-extended derivatives by Pd-catalyzed cross-couplings revealed an enhancement in their inherent electronic property differences, demonstrating the feasibility of such an approach for molecular property tuning.

Photophysical Properties of N-Methyl and N-Acetyl Substituted Alloxazine: A Theoretical Investigation

2021 ◽  
Author(s):  
Huimin Guo ◽  
Xiaolin Ma ◽  
Zhiwen Lei ◽  
Yang Qiu ◽  
Bernhard Dick ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Electronic Structure ◽  
Theoretical Investigation ◽  
Density Functional ◽  
Photophysical Properties ◽  
Time Dependent ◽  
Functional Theory ◽  
Td Dft ◽  
Dependent Density

The electronic structure and photophysical properties of a series of N-Methyl and N-Acetyl substituted alloxazine (AZs) were investigated with extensive density functional theory (DFT) and time-dependent density functional theory (TD-DFT)...

Sign in / Sign up

Export Citation Format

Share Document