Chemical Bonding and Aromaticity in Trinuclear Transition-Metal Halide Clusters

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• 作者：Philippe F. Weck ; Alina P. Sergeeva ; Eunja Kim ; Alexander I. Boldyrev ; Kenneth R. Czerwinski
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：February 7, 2011
• 年：2011
• 卷：50
• 期：3
• 页码：1039-1046
• 全文大小：963K
• 年卷期：v.50,no.3(February 7, 2011)
• ISSN：1520-510X

文摘

Trinuclear transition-metal complexes such as Re₃X₉ (X = Cl, Br, I), with their uniquely featured structure among metal halides, have posed intriguing questions related to multicenter electron delocalization for several decades. Here we report a comprehensive study of the technetium halide clusters [Tc₃(渭-X)₃X₆]^{0/1鈭?2鈭?/sup> (X = F, Cl, Br, I), isomorphous with their rhenium congeners, predicted from density functional theory calculations. The chemical bonding and aromaticity in these clusters are analyzed using the recently developed adaptive natural density partitioning method, which indicates that only [Tc₃X₉]2鈭?/sup> clusters exhibit aromatic character, stemming from a d-orbital-based 蟺 bond delocalized over the three metal centers. We also show that standard methods founded on the nucleus-independent chemical shift concept incorrectly predict the neutral Tc₃X₉ clusters to be aromatic.}