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A DFT study on the mechanisms for gas phase reaction of yttrium with propene
Author(s) -
Li Tao Hong,
Xie Xiao Guang
Publication year - 2010
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1655
Subject(s) - chemistry , propene , propyne , allene , gas phase , yttrium , computational chemistry , reaction mechanism , concerted reaction , stepwise reaction , elimination reaction , medicinal chemistry , photochemistry , catalysis , kinetics , organic chemistry , order of reaction , reaction rate constant , oxide , physics , quantum mechanics
The gas phase reaction of ground‐state yttrium (Y) with propene, previously examined by crossed molecular beams (CMBs) experiment, has been theoretically investigated in detail using B3LYP method. Three concerted and five stepwise pathways were found for H 2 elimination. The calculated PESs indicate that the concerted mechanisms are energetically much more favorable than the stepwise mechanisms for the elimination of H 2 . Three isomers, Y‐propyne, Y‐allene, and Y(CHCHCH 2 ), were assigned to the experimentally observed H 2 ‐elimination product, YC 3 H 4 . Three pathways were identified for the CC bond cleavage products, YCH 2 + C 2 H 4 . The energetically most favorable pathway involves the formation of a metallacyclobutane intermediate, which can decay to YCH 2 + C 2 H 4 . The results of this study confirmed some previous inferences and provided more details for the title reaction. Copyright © 2010 John Wiley & Sons, Ltd.