Ag(III)···Ag(III) Argentophilic Interaction in a Cofacial Corrole Dyad
Ag(III)···Ag(III) Argentophilic Interaction in a Cofacial Corrole Dyad
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Ag(III)····Ag(III) 面科罗勒二元体中的亲银相互作用
DOI：
10.1021/acs.inorgchem.2c02285
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发表时间：
2023
影响因子：
4.6
通讯作者：
Nocera, Daniel G.
中科院分区：
文献类型：
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作者：
Lemon, Christopher M.;Powers, David C.;Huynh, Michael;Maher, Andrew G.;Phillips, Austin A.;Tripet, Brian P.;Nocera, Daniel G.
闭壳金属中心之间的亲金属相互作用以d10离子为例，其中亲金相互作用以Au（I）为原型。这种相互作用延伸到d8物种，并且涉及Au（III）的例子是普遍的。相反，Ag（III）亲银相互作用是不常见的。在这里，我们确定在银corroles，这是真正的银（III）物种的亲银相互作用。单体银咔咯的晶体结构在固态下是二聚体，并且大环表现出非典型的圆顶构象。为了评估这是否代表真实的亲金属相互作用或晶体堆积伪像，制备了类似的共面或“pacman”咔咯。单体的构象在银pacman可咯中重现，金属中心之间的距离为3.67 nm，并显著压缩了咕吨骨架。理论计算支持在pacman络合物中存在罕见的Ag（III）···Ag（III）亲银相互作用。
Metallophilic interactions between closed-shell metal centers are exemplified by d10ions, with Au(I) aurophilic interactions as the archetype. Such an interaction extends to d8species, and examples involving Au(III) are prevalent. Conversely, Ag(III) argentophilic interactions are uncommon. Here, we identify argentophilic interactions in silver corroles, which are authentic Ag(III) species. The crystal structure of a monomeric silver corrole is a dimer in the solid state, and the macrocycle exhibits an atypical domed conformation. In order to evaluate whether this represents an authentic metallophilic interaction or a crystal-packing artifact, the analogous cofacial or “pacman” corrole was prepared. The conformation of the monomer was recapitulated in the silver pacman corrole, exhibiting a short 3.67 Å distance between metal centers and a significant compression of the xanthene backbone. Theoretical calculations support the presence of a rare Ag(III)···Ag(III) argentophilic interaction in the pacman complex.