Hong Jung-Ho, Aslam Adil S, Ko Min-Sung, Choi Jonghoon, Lee Yunho, Cho Dong-Gyu
Department of Chemistry and Chemical Engineering, Inha University, Incheon, 22212, Republic of Korea.
Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon, 3055-701, Republic of Korea.
Chemistry. 2018 Jul 17;24(40):10054-10058. doi: 10.1002/chem.201802176. Epub 2018 Jun 19.
Allyliporphyrin is a carbaporphyrin that has replaced one pyrrole with an allyl group. Dynamic behavior (bond rotation) was observed by variable temperature H NMR and 2D-NOESY NMR spectroscopy and theoretically examined by DFT calculations. These studies revealed that well-defined bond rotation was first observed in the limited space of the carbaporphyrin from 2 through cis-2 and the calculated rotational barrier was low enough, with the relative energy level of cis-2 only 0.65 kcal mol higher than 2. The synthesized allyliporphyrin (2) is a strongly aromatic macrocycle as indicated by the chemical shifts of its inner NH and CH signals. However, its palladium complex displayed reduced aromaticity due to the tilted thiophene of Pd-2.
烯丙基卟啉是一种碳卟啉，其中一个吡咯被烯丙基取代。通过变温氢核磁共振和二维核欧沃豪斯效应光谱观察到了动态行为（键旋转），并通过密度泛函理论计算进行了理论研究。这些研究表明，首先在碳卟啉从2经由顺式-2的有限空间中观察到了明确的键旋转，并且计算出的旋转势垒足够低，顺式-2的相对能级仅比2高0.65千卡/摩尔。合成的烯丙基卟啉（2）是一种强芳香性大环化合物，这由其内部NH和CH信号的化学位移表明。然而，由于Pd-2中噻吩的倾斜，其钯配合物的芳香性降低。
