Oriented internal electrostatic fields: an emerging design element in coordination chemistry and catalysis.
Oriented internal electrostatic fields: an emerging design element in coordination chemistry and catalysis.
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DOI：
10.1039/d2sc01715f
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发表时间：
2022-05-18
期刊：
影响因子：
8.4
通讯作者：
Tomson, Neil C.
中科院分区：
文献类型：
--
作者：
Weberg, Alexander B.;Murphy, Ryan P.;Tomson, Neil C.
定向静电场(ESF)对化学键和反应活性的影响是一个迅速引起人们关注的现象。最近，强ESFS的存在被认为是部分酶活性的最重要贡献因素之一，其中底物的变化偶极矩与强大的局部静电场的排列被证明是导致酶速率提高的主要原因。在酶学之外，研究人员通过在反应中添加离子盐和在有机分子中加入带电官能团(通过实验和计算)，以及通过在电极板之间实施体积场来“外部”研究“内部”静电场的影响。将带电部分结合到均相无机络合物中以生成内部ESF是新型催化剂设计的一个很有潜力的领域。这一领域在过去10年内才开始实现，但可能是一个具有重大影响的领域，因为它提供了一种手段，通过与传统策略正交的方法来调整分子络合物的性质，从而为改善催化条件和新颖的反应活性提供了可能性。从这一角度来看，我们重点介绍了这一领域的最新发展，并提供了从我们自己的研究中获得的关于这一新兴研究领域的挑战和未来方向的见解。内静电场效应将在分子配位络合物和催化剂的设计中发挥重要作用。
The power of oriented electrostatic fields (ESFs) to influence chemical bonding and reactivity is a phenomenon of rapidly growing interest. The presence of strong ESFs has recently been implicated as one of the most significant contributors to the activity of select enzymes, wherein alignment of a substrate's changing dipole moment with a strong, local electrostatic field has been shown to be responsible for the majority of the enzymatic rate enhancement. Outside of enzymology, researchers have studied the impacts of “internal” electrostatic fields via the addition of ionic salts to reactions and the incorporation of charged functional groups into organic molecules (both experimentally and computationally), and “externally” via the implementation of bulk fields between electrode plates. Incorporation of charged moieties into homogeneous inorganic complexes to generate internal ESFs represents an area of high potential for novel catalyst design. This field has only begun to materialize within the past 10 years but could be an area of significant impact moving forward, since it provides a means for tuning the properties of molecular complexes via a method that is orthogonal to traditional strategies, thereby providing possibilities for improved catalytic conditions and novel reactivity. In this perspective, we highlight recent developments in this area and offer insights, obtained from our own research, on the challenges and future directions of this emerging field of research. Internal electrostatic field effects are poised to play a major role in the design of molecular coordination complexes and catalysts.
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影响因子：
4.6
作者：
Dhar D;Yee GM;Tolman WB
通讯作者：
Tolman WB
高反应性P450模型化合物I。
影响因子：
15
作者：
Bell, Seth R.;Groves, John T.
通讯作者：
Groves, John T.
影响因子：
--
作者：
Bottcher, A;Grinstaff, MW;Gray, HB
通讯作者：
Gray, HB
DOI：
10.1126/science.1259802
发表时间：
2014-12-19
期刊：
Science (New York, N.Y.)
影响因子：
--
作者：
Fried SD;Bagchi S;Boxer SG
通讯作者：
Boxer SG
影响因子：
--
作者：
Bottcher, A;Birnbaum, ER;Labinger, JA
通讯作者：
Labinger, JA