Olefin epoxidation by molybdenum peroxo compound: molecular mechanism characterized by the electron localization function and catastrophe theory.
Olefin epoxidation by molybdenum peroxo compound: molecular mechanism characterized by the electron localization function and catastrophe theory.
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钼过氧化合物的烯烃环氧化：以电子定位功能和突变理论为特征的分子机制。
DOI：
10.1021/jp108440f
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发表时间：
2011
期刊：
影响因子：
--
通讯作者：
V. S. Safont
中科院分区：
文献类型：
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作者：
S. Berski;F. Sensato;V. Polo;J. Andrés;V. S. Safont
在键演化理论的框架下，研究了mimon型络合物MoO(η(2)-O(2))(2)OPH(3)向乙烯C(2)H(4)的氧原子转移反应，得到氧环C(2)H(4)O，并用电子定位函数的拓扑分析（ELF）和Thom突变理论（CT）表征了相应的分子机理。ELF拓扑分析和电子密度分析表明，MoO(η(2)-O(2))(2)OPH(3)和MoO(2)(η(2)-O(2))OPH(3)中的所有Mo-O键都属于闭壳型相互作用，尽管总能量密度E(E)（r(BCP)）为负值暗示有一定的共价贡献。过氧O(i)-O(j)键具有电荷移位或原共价键的特征，其中单突触键对V(3)(O(i))， V(3)（O(j)）具有小的电子居群，每个约0.25e，位于核心键C(O(i))， C（O(j)）之间。钼二过氧络合物MoO(η(2)-O(2))(2)OPH(3)到C(2)H(4)体系的氧转移反应可以用以下连续的化学事件来描述：(a)原共价过氧O(2)-O(1)键断裂，(b)乙烯中双C(1)=C(2)键还原为单C(1)-C(2)键，(C)氧O(1)被两个非成键盆地V(i=1,2)（O(1)）取代，(d)非成键盆地增加到三个(V(i=1,2,4)(O(1))；(e)重组和减少非键基的数量，形成两个盆地(V(i=1,4)(O(1))，类似于氧环烷中非键电子密度的elf拓扑结构，(e)氧环烷中第一个O(1)-C(2)键的形成，(f) C(2)-O(1)-C(2)环闭合，(g)新Mo=O(2)键中单一非键盆地V（O(2)）的形成。氧原子以阴离子的形式转移，携带一个很小的电子电荷，从0.5到0.7e不等。
The oxygen atom transfer reaction from the Mimoun-type complex MoO(η(2)-O(2))(2)OPH(3) to ethylene C(2)H(4) affording oxirane C(2)H(4)O 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))(2)OPH(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(j)) 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))(2)OPH(3) to C(2)H(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)(O(1))); (e) reorganization and reduction in the number of nonbonding basis to two basins (V(i=1,4)(O(1))) 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.