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Theoretical study of mechanism of extraction reaction between germylene carbene and its derivatives and thiirane
Author(s) -
Lu Xiu Hui,
Che Xin,
Shi Le Yi,
Han Jun Feng,
Xia Lian Zhen
Publication year - 2011
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.22621
Subject(s) - thiirane , chemistry , carbene , electronegativity , substituent , transition state , computational chemistry , density functional theory , singlet state , reaction mechanism , photochemistry , crystallography , medicinal chemistry , ring (chemistry) , catalysis , organic chemistry , atomic physics , physics , excited state
The mechanism of the sulfur extraction reaction between singlet germylene carbene and its derivatives [X 2 GeC: (X = H, F, Cl, CH 3 )] and thiirane has been investigated with density functional theory, including geometry optimization and vibrational analyses for the involved stationary points on the potential energy surface. The energies of the different conformations are calculated by B3LYP/6‐311G(d,p) method. From the potential energy profile, it can be predicted that the reaction pathway of this kind consists two steps: (1) the two reactants firstly form an intermediate (INT) through a barrier‐free exothermic reaction; (2) the INT then isomerizes to a product via a transition state (TS). This kind reaction has similar mechanism, when the germylene carbene and its derivatives [X 2 GeC: (X = H, F, Cl, CH 3 )] and thiirane get close to each other, the shift of 3 p lone electron pair of S in thiirane to the 2 p unoccupied orbital of C in X 2 Ge = C: gives a p → p donor–acceptor bond, leading to the formation of INT. As the p → p donor–acceptor bond continues to strengthen (that is the CS bond continues to shorten), the INT generates product (P + C 2 H 4 ) via TS. It is the substituent electronegativity that mainly affects the extraction reactions. When the substituent electronegativity is greater, the energy barrier is lower, and the reaction rate is greater. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011