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Calculations on the Polymerization Process of Some 1,1‐Disubstituted Cyclopropanes: I. The Initiation Step
Author(s) -
Peeters Daniel,
Leroy Georges
Publication year - 1998
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/(sici)1099-0690(199807)1998:7<1397::aid-ejoc1397>3.0.co;2-h
Subject(s) - chemistry , polymerization , kinetic energy , ab initio , computational chemistry , reaction mechanism , process (computing) , electronic correlation , ab initio quantum chemistry methods , thermodynamics , catalysis , organic chemistry , polymer , molecule , classical mechanics , physics , computer science , operating system
Ab initio calculations on the initial steps of the polymerization process of 1,1‐dicyano‐, ‐difluoro‐ and ‐di‐methyl‐substituted cyclopropanes are presented. Polyme‐rization enthalpies determined by model calculations show the thermodynamic feasibility of the process. The reaction mechanism of the first step is further discussed by considering initiation by various species such as H q , OH q , and CH 3 q (q = +, 0, –). Transition structures and energy barriers are obtained for all species, allowing discussion of the reaction mechanism and an estimation of the kinetic feasibility. The Hartree–Fock structures at the 6‐31+G(d, p) level have been fully optimized and electron correlation has been introduced at the MP2 level for some selected reaction mechanisms.