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Unexpected Molecular Structure of a Putative Rhenium-Dioxo-Benzocarbaporphyrin Complex. Implications for the Highest Transition Metal Valence in a Porphyrin-Type Ligand Environment.
ChemistryOpen ( IF 2.3 ) Pub Date : 2019-10-18 , DOI: 10.1002/open.201900271
Abraham B Alemayehu 1 , Hugo Vazquez-Lima 2 , Simon J Teat 3 , Abhik Ghosh 1
Affiliation  

A combination of quantum chemical calculations and synthetic studies was used to address the possibility of very high (>6) valence states of transition metals in porphyrin‐type complexes. With corrole as a supporting ligand, DFT calculations ruled out Re(VII) and Ir(VII) dioxo complexes as stable species. Attempted rhenium insertion into benzocarbaporphyrin (BCP) ligands on the other hand led to two products with different stoichiometries – Re[BCP]O and Re[BCP]O2. To our surprise, single‐crystal structure determination of one of the complexes of the latter type indicated an ReVO center with a second oxygen bridging the Re−C bond. In other words, although the monooxo complexes Re[BCP]O are oxophilic, the BCP ligand cannot sustain a trans‐ReVII(O)2 center. The search for metal valence states >6 in porphyrin‐type ligand environments must therefore continue.

中文翻译:

推定的铼-二氧代-苯并碳卟啉复合物的意外分子结构。卟啉型配体环境中最高过渡金属价的影响。

量子化学计算和合成研究相结合,用于解决卟啉型配合物中过渡金属非常高(> 6)价态的可能性。以咔咯作为支持配体,DFT 计算排除了 Re(VII) 和 Ir(VII) 二氧配合物作为稳定物质。另一方面,尝试将铼插入苯并碳卟啉 (BCP) 配体中,产生了两种具有不同化学计量的产物 – Re[BCP]O 和 Re[BCP]O 2。令我们惊讶的是,后一种类型的配合物之一的单晶结构测定表明 Re V O 中心具有桥接 Re−C 键的第二个氧。换句话说,虽然单氧配合物Re[BCP]O是亲氧性的,但BCP配体不能维持反式-Re VII (O) 2中心。因此,必须继续在卟啉型配体环境中寻找> 6 的金属价态。
更新日期:2019-10-18
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