Sessler Jonathan L, Tomat Elisa
Department of Chemistry and Biochemistry, 1 University Station A-5300, The University of Texas at Austin, Austin, Texas 78712, USA.
Acc Chem Res. 2007 May;40(5):371-9. doi: 10.1021/ar600006n. Epub 2007 Mar 31.
Over the last 2 decades, the rapid development of new synthetic routes for the preparation of expanded porphyrin macrocycles has allowed for the exploration of a new frontier consisting of "porphyrin-like" coordination chemistry. In this Account, we summarize our exploratory forays into the still relatively poorly explored area of oligopyrrolic macrocycle metalation chemistry. Specifically, we describe our successful formation of both mono- and binuclear complexes and, in doing so, highlight the diversity of coordination modes available to expanded porphyrin-type ligands. The nature of the inserted cation, the emerging role of tautomeric equilibria, and the importance of hydrogen-bonding interactions in regulating this chemistry are also discussed.
在过去的20年里，用于制备扩展卟啉大环化合物的新合成路线迅速发展，使得人们能够探索一个由“类卟啉”配位化学组成的新领域。在本综述中，我们总结了我们在寡聚吡咯大环金属化化学这一仍相对未被充分探索的领域中的探索尝试。具体而言，我们描述了我们成功形成单核和双核配合物的过程，并在此过程中强调了扩展卟啉型配体可用的配位模式的多样性。还讨论了插入阳离子的性质、互变异构平衡的新作用以及氢键相互作用在调节这种化学过程中的重要性。
