کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
1325471 1499875 2014 8 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Quantum-chemical study of organic reaction mechanisms. Part 2. Addition of selenium dichloride to acetylene
ترجمه فارسی عنوان
مطالعه کوانتومی شیمیایی مکانیسم واکنش آلی. قسمت 2. اضافه کردن دی کلرید سلنیوم به استیلن
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی معدنی
چکیده انگلیسی


• The mechanism of the addition of selenium dichloride to acetylene has been theoretically studied.
• The reaction proceeds via a selenirenium intermediate with the four-coordinated selenium atom.
• The intermediate exhibits a trigonal-bipyramidal configuration.
• The obtained results are in good agreement with the experimental data.

The mechanism of the addition of selenium dichloride to acetylene has been studied theoretically at the DFT-B3LYP/6-311+G(d,p) level. The reaction proceeds as anti-anti-addition via the formation of the intermediate selenirenium compounds with the four-coordinated selenium atom. Both thermodynamically and kinetically, a favorable E-2-chloroselenenyl chloride is formed on the first stage of the reaction. The experimentally observed E,E-bis(2-chlorovinyl) selenide is kinetically more favorable as compared to E,Z-isomer. Possible alternative reaction mechanisms require much higher energy barriers. Stereoselectivity of the process is achieved through the kinetic control of the reaction. In the reaction profile of a preferable route leading to a kinetically favorable E,E-bis(2-chlorovinyl) selenide the entropy factor doesn't play a major role in the energetics of both stages.

The reaction of selenium dichloride with acetylene proceeds as anti-anti-addition via the formation of intermediate selenirenium compounds with the four-coordinated selenium atom.Figure optionsDownload as PowerPoint slide

ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Journal of Organometallic Chemistry - Volume 766, 1 September 2014, Pages 49–56
نویسندگان
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