Trigger bond analysis of nitroaromatic energetic materials using wiberg bond indices

MP2/6-31G(d) was employed to investigate the theoretical calculations on the pyrolysis of alkyl methyl (thion)carbonates, where alkyl groups referred to ethyl, isopropyl and t-butyl groups. Nine possible pathways were considered for the pyrolysis of alkyl methyl thioncarbonates, while only seven possible pathways were found to pyrolyze alkyl methyl carbonates. Both of them had three pathways to generate the desired alkene products. Not only thermal elimination pathways were calculated, other possible mechanisms, such as rearrangements and nucleophilic substitutions, were also considered. The progress of the reactions was also investigated by the calculation of Wiberg bond indices at MP2/6-31G(d) level.

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A computational study on the thermal decomposition of di(tri)thiocarbonates

Journal of Theoretical and Computational Chemistry ◽

10.1142/s0219633616500619 ◽

2016 ◽

Vol 15 (07) ◽

pp. 1650061 ◽

Cited By ~ 3

Author(s):

Jingjing Xia ◽

Ping Wu

Keyword(s):

Thermal Decomposition ◽

Computational Study ◽

Theoretical Calculations ◽

Reaction Progress ◽

Bond Indices ◽

Elimination Reactions ◽

Wiberg Bond Indices

Alkyl methyl di(tri)thiocarbonates can be thermally decomposed into alkenes. In this paper, theoretical calculations were used to calculate the thermal decomposition procedures. Six compounds, including ethyl, isopropyl and [Formula: see text] dithiocarbonate and trithiocarbonate, were examined. For each decomposition, nine possible paths were considered, including the paths leading to the desired alkene products, as well as rearrangement and elimination reactions. This calculation was performed with the MP2/6-31G(d) method. Wiberg bond indices were also calculated to further reveal the reaction progress.

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A theoretical study towards thermolysis process of thionesters and thiolesters

Journal of Theoretical and Computational Chemistry ◽

10.1142/s0219633618500141 ◽

2018 ◽

Vol 17 (02) ◽

pp. 1850014 ◽

Cited By ~ 3

Author(s):

Xun Zhu ◽

Xiuqin Zhou ◽

Dongsheng Xiang ◽

Ping Wu

Keyword(s):

Theoretical Study ◽

Theoretical Calculations ◽

Transition States ◽

Membered Ring ◽

Basis Set ◽

Reaction Progress ◽

Alkyl Groups ◽

Thermal Elimination ◽

Bond Indices ◽

Wiberg Bond Indices

This paper focuses on the thermal elimination of alkenes from methyl alkyl thionacetates and thiolacetates. Three alkyl groups are calculated: ethyl, isopropyl and tert-butyl. Possible elimination mechanisms are considered, including six- and four-membered ring transition states for alkene elimination, four-membered ring isomerization and a possible five-membered ring decomposition. Theoretical calculations are performed with the MP2 method and the 6-31G* basis set. Wiberg bond indices are also summarized to monitor the reaction progress.

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