کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
5417779 | 1506958 | 2007 | 10 صفحه PDF | دانلود رایگان |
The mechanisms for the insertion of alkylidenecarbenes into OH bond of water have been investigated with B3LYP/6-311G(d,p) method. The XYCCÂ +Â H2O (XYCC: H2CC, HFCC, HClCC, HBrCC, H(CH3)CC, F2CC, Cl2CC, Br2CC, (CH3)2CC) system is the subject of the present study. According to our model calculations these insertion reactions can yield vinyl alcohol products and for a given single substituted alkylidenecarbene will yield cis-trans-isomer mixtures. Moreover the reactivity of alkylidenecarbene decreases in the order: HFCCÂ >Â HClCCÂ >Â HBrCCÂ >Â H(CH3)CCÂ >Â H2CC. The same phenomenon can be found in double substituted alkylidenecarbene, that is, F2CCÂ >Â Cl2CCÂ >Â Br2CCÂ >Â (CH3)2CCÂ >Â H2CC. Our theoretical findings suggest that the singlet-triplet splitting (ÎEST) of the XYCC species can be used as a guide to predict its activity for insertion reactions.
Journal: Journal of Molecular Structure: THEOCHEM - Volume 821, Issues 1â3, 1 November 2007, Pages 106-115