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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Olefin epoxidation by molybdenum peroxo compound: Molecular mechanism characterized by the electron localization function and catastrophe theory
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Olefin epoxidation by molybdenum peroxo compound: Molecular mechanism characterized by the electron localization function and catastrophe theory

机译：过氧钼化合物对烯烃的环氧化作用：以电子定位功能和突变理论为特征的分子机理

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摘要

The oxygen atom transfer reaction from the Mimoun-type complex MoO (η~2-O_2)_2OPH_3 to ethylene C _2H_4 affording oxirane C_2H_4O has been investigated within the framework of the Bonding Evolution Theory in which the corresponding molecular mechanism is characterized by the topological analysis of the electron localization function (ELF) and Thom's catastrophe theory (CT). Topological analysis of ELF and electron density analysis reveals that all Mo-O bonds in MoO(η~2-O_2)_2OPH_3 and MoO_2(η~2-O_2)OPH_3 belong to closed-shell type interactions though negative values of total energy densities E~e(r_(BCP)) imply some covalent contribution. The peroxo O_i-O_j bonds are characterized as charge-shift or protocovalent species in which pairs of monosynaptic basins V_3(O _i), V_3(O_((pj)) with a small electron population of ～0.25e each, are localized between core basins C(O_i), C(O _j). The oxygen transfer reaction from molybdenum diperoxo complex MoO(η~2-O_2)_2OPH_3 to C _2H_4 system can be described by the following consecutive chemical events: (a) protocovalent peroxo O_2-O_1 bond breaking, (b) reduction of the double C_1=C_2 bond to single C_1-C_2 bond in ethylene, (c) displacement of oxygen O _1 with two nonbonding basins, V_(i=1,2)(O_1), (d) increase of a number of the nonbonding basins to three (V _(i=1,2,4)(O1)); (e) reorganization and reduction in the number of nonbonding basis to two basins (V_(i=1,4)(O1)) resembling the ELF-topology of the nonbonding electron density in oxirane, (e) formation of the first O_1-C_2 bond in oxirane, (f) C _2-O_1-C_2 ring closure, (g) formation of singular nonbonding basin V(O_2) in new Mo=O_2 bond. The oxygen atom is transferred as an anionic moiety carrying a rather small electronic charge ranging from 0.5 to 0.7e.
机译：在键合演化理论的框架内研究了由Mimoun型配合物MoO（η〜2-O_2）_2OPH_3到提供环氧乙烷C_2H_4O的乙烯C _2H_4的氧原子转移反应，其中相应的分子机理通过拓扑分析表征电子本地化函数（ELF）和Thom的突变理论（CT）的描述。 ELF的拓扑分析和电子密度分析表明，尽管总能量密度E为负值，但MoO（η〜2-O_2）_2OPH_3和MoO_2（η〜2-O_2）OPH_3中的所有Mo-O键均属于闭壳型相互作用。 〜e（r_（BCP））暗示一些共价贡献。过氧O_i-O_j键的特征是电荷转移或原价共价物种，其中成对的单突触盆地V_3（O _i），V_3（O _（（pj））各自具有约0.25e的小电子种群，位于核之间从二茂钼配合物MoO（η〜2-O_2）_2OPH_3到C _2H_4体系的氧转移反应可以通过以下连续的化学事件来描述：（a）原价过氧化物O_2- O_1键断裂，（b）在乙烯中将双C_1 = C_2键还原为单C_1-C_2键，（c）用两个非键合盆V_（i = 1,2）（O_1）置换氧O _1，（ d）将非粘结盆地的数量增加到三个（V _（i = 1,2,4）（O1））;（e）重组并减少两个盆地的非粘结基础的数量（V_（i = 1 ，4）（O1））类似于环氧乙烷中非键电子密度的ELF拓扑，（e）环氧乙烷中第一个O_1-C_2键的形成，（f）C _2-O_1-C_2闭环，（g）的形成新奇异非粘结盆地V（O_2） Mo ＝ O_2键。氧原子作为阴离子部分转移，带有0.5至0.7e的相当小的电子电荷。

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