Department of Chemistry, Carleton College, Northfield, MN, United States.
Beilstein J Org Chem. 2012;8:1554-63. doi: 10.3762/bjoc.8.177. Epub 2012 Sep 18.
The concept of frustrated Lewis pairs (FLPs) has received considerable attention of late, and numerous reports have demonstrated the power of non- or weakly interacting Lewis acid-base pairs for the cooperative activation of small molecules. Although most studies have focused on the use of organic or main-group FLPs that utilize steric encumbrance to prevent adduct formation, a related strategy can be envisioned for both organic and inorganic complexes, in which "electronic frustration" engenders reactivity consistent with both nucleophilic (basic) and electrophilic (acidic) character. Here we propose that such a description is consistent with the behavior of many coordinatively unsaturated transition-metal species featuring metal-ligand multiple bonds, and we further demonstrate that the resultant reactivity may be a powerful tool for the functionalization of C-H and E-H bonds.
近来，受阻路易斯对（FLP）的概念受到了相当多的关注，许多报道都证明了非或弱相互作用的路易斯酸碱对在协同活化小分子方面的强大功能。尽管大多数研究都集中在使用有机或主族 FLP 上，这些 FLP 利用空间位阻来防止加合物的形成，但对于有机和无机配合物，也可以设想一种类似的策略，其中“电子受阻”产生与亲核（碱性）和亲电（酸性）特性一致的反应性。在这里，我们提出这样的描述与许多配位不饱和过渡金属物种的行为是一致的，这些物种具有金属-配体多重键，我们进一步证明，由此产生的反应性可能是 C-H 和 E-H 键功能化的有力工具。
