Electronic structure and UV spectra of N-arylthio-1,4-benzoquinone imines

Journal Article · Wed Jan 01 04:00:00 EST 1986 · Theor. Exp. Chem. (Engl. Transl.); (United States)

OSTI ID:6011200

Pirozhenko, V V; Boldeskul, I E; Kolesnikov, V T; Vid, L V; Kuz'menko, L O

The electronic structure of N-arylthio-1,4-benzoquinone imines (II) was studied by quantum-chemical methods (CNDO/2). It was shown that the special characteristics of the reactivity of the compounds in reaction with chlorine compared with sulfenylketimines R/sub 2/C=N-S-Ar not containing a quinonoid ring may be due to the different nature of the lowest unoccupied molecular orbitals (LUMO). The UV spectra of compounds (II) were investigated. In the visible region the spectra of all the compounds contain strong absorption (R/sub 1/ = R/sub 2/ = R/sub 3/ = R/sub 4/ = R/sub 5/ = H, lambda/sub m/ = 433 nm, epsilon/sub m/ = 2.12 x 10/sup 4/ liters/mole x cm), due to intramolecular charge transfer from the sulfur atom to the quinonoid fragment of the molecule. It was established that there is a linear relation between the energy of the transition and the sigma/sup +/ constants of the substituents in the aryl fragment. The assignment of the transitions was confirmed by calculations of the UV spectra of N-arylthio-1,4-benzoquinone imines by the PPP method. Comparison of the UV spectra of these compounds with the UV spectra of N-arylsulfonyl-1,4-benzoquinone imines makes it possible to conclude that the sulfur atom of the SO/sub 2/ group, unlike the divalent sulfur atom, is not capable of transmitting the electronic effects of the substituents from one part of the molecule to the other.

• Research Organization: Institute of Organic Chemistry, Kiev, USSR
• OSTI ID: 6011200
• Journal Information: Theor. Exp. Chem. (Engl. Transl.); (United States), Journal Name: Theor. Exp. Chem. (Engl. Transl.); (United States) Vol. 21:4; ISSN TEXCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
640302* -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
ABSORPTION SPECTRA
ACTIVATION ENERGY
AROMATICS
ATOMIC MODELS
BENZOQUINONES
BINDING ENERGY
CHARGE DISTRIBUTION
CHEMICAL REACTIONS
CHLORINATION
CHLORINE
COMPUTERIZED SIMULATION
CONFIGURATION INTERACTION
ELECTRON TRANSFER
ELECTRONIC STRUCTURE
ELECTRONS
ELEMENTARY PARTICLES
ELEMENTS
ENERGY
ENERGY-LEVEL TRANSITIONS
FERMIONS
HALOGENATION
HALOGENS
IMINES
LEPTONS
MATHEMATICAL MODELS
MECHANICS
NONMETALS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
QUANTUM MECHANICS
QUINONES
SIMULATION
SPECTRA
SPECTRAL SHIFT
THIOLS
ULTRAVIOLET SPECTRA
VALENCE