Ab initio calculations of potential energy surface for reaction of nucleophilic addition of H/sup -/ ion to methylacetylene (in Russian)
Within the framework of the Hartree-Fock-Roothaan Method, using double-xi basis sets 3-21++G and (6-31++G//3-21++G), the minimum energy paths (MEPs) have been calculated for reactions of nucleophilic addition of the hydride ion H/sup -/ to the methylacetylene molecule: CH/sub 3/-C triple bond CH + H/sup -/ ..-->.. (CH/sub 3/-CH=CH)/sup -/ (1) CH/sub 3/-C triple bond CH + H/sup -/ ..-->.. (CH/sub 3/-C=CH/sub 2/)/sup -/ (2). It has been established that the activation energy for reaction (2) is 7.02 kJ/mole lower than for reaction (1). An analysis has been made of the character of electron density distribution along the MEP of each reaction. It has been shown that distortion of geometry of the reactants plays an important role in intensifying the interaction of the frontier orbitals. The reasons for nonfulfillment of Markownikoff's rule for these reactions have been determined. The results from the calculations are compared with calculations reported in the literature for the related reaction of nucleophilic addition of the hydride ion H/sup -/ to the acetylene molecule: HC triple bond CH + H/sup -/ ..cap alpha.. (CH/sub 2/=CH)/sup -/.
- Research Organization:
- M. V. Lomonosov Moscow Institute of Fine-Chemical Technology, USSR
- OSTI ID:
- 6387223
- Journal Information:
- Theor. Exp. Chem. (Engl. Transl.); (United States), Vol. 21:3; Other Information: Translated from Teor. Eksp. Khim.; 21: No. 3, 303-309(May-Jun 1985)
- Country of Publication:
- United States
- Language:
- Russian
Similar Records
The synthesis, characterization, and reactivity of some alkyne, vinylidene, and butatrienylidene complexes of ruthenium
Photodissociation of methylacetylene at 193 nm
Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
74 ATOMIC AND MOLECULAR PHYSICS
HYDROGEN COMPOUNDS
ATOMIC MODELS
CHEMICAL REACTION KINETICS
PROPYNE
POTENTIAL ENERGY
ACTIVATION ENERGY
BINDING ENERGY
COMPUTERIZED SIMULATION
CONFIGURATION INTERACTION
EFFECTIVE CHARGE
ELECTRON DENSITY
ELECTRON TRANSFER
ELECTRONIC STRUCTURE
G CODES
GAUSS FUNCTION
HARTREE-FOCK METHOD
HYDRIDATION
HYDROGEN TRANSFER
PERTURBATION THEORY
POLYATOMIC MOLECULES
QUANTUM MECHANICS
REACTION HEAT
ALKYNES
CHEMICAL REACTIONS
COMPUTER CODES
ENERGY
ENTHALPY
FUNCTIONS
HYDROCARBONS
KINETICS
MATHEMATICAL MODELS
MECHANICS
MOLECULES
ORGANIC COMPOUNDS
PHYSICAL PROPERTIES
REACTION KINETICS
SIMULATION
THERMODYNAMIC PROPERTIES
400201* - Chemical & Physicochemical Properties
640302 - Atomic
Molecular & Chemical Physics- Atomic & Molecular Properties & Theory