Near-IR Absorbing Nickel(II) Porphyrinoids Prepared by Regioselective Insertion of Silylenes into Antiaromatic Nickel(II) Norcorrole
Near-IR Absorbing Nickel(II) Porphyrinoids Prepared by Regioselective Insertion of Silylenes into Antiaromatic Nickel(II) Norcorrole
复制标题
DOI：
10.1002/anie.201309921
复制
发表时间：
2014-02-03
影响因子：
16.6
通讯作者：
Shinokubo, Hiroshi
中科院分区：
文献类型：
--
作者：
Fukuoka, Takaki;Uchida, Kenya;Shinokubo, Hiroshi
用动力学稳定的硅烯处理反芳香降咯Ni-II配合物，通过高度的区域选择性和立体选择性插入-吡咯CC键，获得了产率很高的扩环产物。所得的Ni-II类卟啉单插入产物尽管被硅原子破坏了环共轭，但由于HOMO-LUMO间隙较小，表现出较强的近红外吸收带。
The treatment of an antiaromatic norcorrole Ni-II complex with a kinetically stabilized silylene provided ring-expansion products in excellent yields through the highly regio- and stereoselective insertion into the - pyrrolic CC bonds. The resultant Ni-II porphyrinoid monoinsertion product exhibited relatively strong near-IR absorption bands due to the small HOMO-LUMO gap in spite of the disrupted cyclic -conjugation by the silicon atom.