Mass spectrometry and quantum chemical studies of the reaction of divinyl telluride with secondary phosphine sulfides: Synthesis of adducts

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• 作者：Nina K. Gusarova ; Nataliya A. Chernysheva ; Lyudmila V. Klyba ; Vladimir A. Shagun ; Svetlana V. Yas'ko ; Vladimir I. Smirnov ; Boris A. Trofimov
• 关键词：Divinyl telluride ; Diphenylphosphine sulfide ; Adducts ; Mass spectra ; Quantum chemical calculations
• 刊名：Journal of Organometallic Chemistry
• 出版年：2013
• 出版时间：15 November, 2013
• 年：2013
• 卷：745-746
• 期：Complete
• 页码：126-132
• 全文大小：1407 K

文摘

Mass spectrometry and quantum chemical studies of the reaction of divinyl telluride with diphenylphosphine sulfide have been carried out. Reaction proceeds under radical initiation (AIBN, 63-68?¡ã§³, 2.5?h, THF, reactants molar ratio?=?1:1) to afford the anti-Markovnikov monoadduct 1 and diadduct 2 in 67 and 23 % yield, respectively. The former easily decomposes to give vinyldiphenylphosphine sulfide 3 (in 63 % yield), ethylene and elemental tellurium, the structure of which represents mainly nano-sized powder consisting of agglomerates with average size of 350-450?nm. The comparative analysis of electron ionization mass spectra of compounds 1, 2 and 3 indicates that the presence of tellurium atom in adducts 1 and 2 reduces stability of their molecular ions and hinders the elimination of sulfur atom. Under conditions of chemical ionization of phosphine sulfides 1 and 3, the process of their protonation with CH₅⁺ followed by the elimination of sulfur atom from [§¯§®]⁺ ion is dominant. These data are also confirmed by the results of quantum chemical calculations of the most stable protonated structures of phosphine sulfides 1 and 3.