Electronic Structure and Conformation Properties of Halogen -Substituted Acetyl Acrylic Anhydrides, CX3C(O)OC(O)CH鈺怌H2 (X = H, F, or Cl)

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• 作者：Wang XiaoPeng ; Tong ShengRui ; Wang WeiGang ; Ge MaoFa ; Wang DianXun
• 刊名：The Journal of Physical Chemistry A
• 出版年：2012
• 出版时间：January 12, 2012
• 年：2012
• 卷：116
• 期：1
• 页码：560-570
• 全文大小：548K
• 年卷期：v.116,no.1(January 12, 2012)
• ISSN：1520-5215

文摘

Acetyl acrylic anhydride (CH₃C(O)OC(O)CHCH₂) and its halogen-substituted derivatives (CF₃C(O)OC(O)CHCH₂ and CCl₃C(O)OC(O)CHCH₂) were prepared by the heterogeneous reaction of gaseous CH₂鈺怌HC(O)Cl with CX₃C(O)OAg (X = H, F, or Cl). The molecular conformations and electronic structure of these three compounds were investigated by HeI photoelectron spectroscopy, photoionization mass spectroscopy, FT-IR, and theoretical calculations. They were theoretically predicted to prefer the [ss-c] conformation, with each C鈺怬 bond syn with respect to the opposite O鈥揅 bond and the C鈺怌 bond in cis orientation to the adjacent C鈺怬 bond. The experimental first vertical ionization potential for CH₃C(O)OC(O)CHCH₂, CF₃C(O)OC(O)CHCH₂, and CCl₃C(O)OC(O)CHCH₂ was determined to be 10.91, 11.42, and 11.07 eV, respectively. In this study, the rule of the conformation properties of anhydride XC(O)OC(O)Y was improved by analyzing the different conformations of anhydrides with various substitutes.