Berti Beatrice, Ciabatti Iacopo, Femoni Cristina, Iapalucci Maria Carmela, Zacchini Stefano
Dipartimento di Chimica Industriale "Toso Montanari", Università di Bologna, Viale Risorgimento 4, I-40136 Bologna, Italy.
ACS Omega. 2018 Oct 16;3(10):13239-13250. doi: 10.1021/acsomega.8b02109. eCollection 2018 Oct 31.
This article describes a rare case of cluster core isomerism in a large molecular organometallic nanocluster. In particular, two isomers of the [HCoPdC(CO)] nanocluster, referred as TP-Pd and Oh-Pd, have been structurally characterized by single-crystal X-ray crystallography as their [NMe(CHPh)][HCoPdC(CO)]·CHCl (ca. 1:1 TP-Pd and Oh-Pd mixture), [NMe(CHPh)][HCoPdC(CO)]·2CHCl (mainly TP-Pd), [NEt(CHPh)][HCoPdC(CO)]·CHCl (mainly TP-Pd), [MePPh][HCoPdC(CO)]·2.5CHCl (mainly TP-Pd), and [MePPh][HCoPdC(CO)] (Oh-Pd) salts. The cluster core of TP-Pd is a tricapped trigonal prism, whereas this is a tricapped octahedron in Oh-Pd. The presence in the solid state of the Oh-Pd or TP-Pd isomers depends on the cation employed and/or the number and type of co-crystallized solvent molecules. Often, mixtures of the two isomers, within the same single crystal or as mixtures of different crystals within the same crystallization batch, are obtained. Structural isomerism in organometallic nanoclusters is discussed and compared to that in Au-thiolate nanoclusters.
本文描述了一个大分子有机金属纳米团簇中罕见的簇核异构现象。具体而言，[HCoPdC(CO)]纳米团簇的两种异构体，即TP-Pd和Oh-Pd，已通过单晶X射线晶体学对其[NMe(CHPh)][HCoPdC(CO)]·CHCl（约1:1的TP-Pd和Oh-Pd混合物）、[NMe(CHPh)][HCoPdC(CO)]·2CHCl（主要为TP-Pd）、[NEt(CHPh)][HCoPdC(CO)]·CHCl（主要为TP-Pd）、[MePPh][HCoPdC(CO)]·2.5CHCl（主要为TP-Pd）和[MePPh][HCoPdC(CO)]（Oh-Pd）盐进行了结构表征。TP-Pd的簇核是一个三帽三棱柱，而在Oh-Pd中则是一个三帽八面体。Oh-Pd或TP-Pd异构体在固态中的存在取决于所使用的阳离子和/或共结晶溶剂分子的数量和类型。通常，会得到同一单晶内两种异构体的混合物，或者同一结晶批次中不同晶体的混合物。本文讨论了有机金属纳米团簇中的结构异构现象，并将其与金硫醇盐纳米团簇中的异构现象进行了比较。
