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Atom-Precise Organometallic Zinc Clusters

Abstract : The bottom-up synthesis of organometallic zinc clusters is described. The cation \[Zn10 ](Cp*)6 Me\(+) (1) is obtained by reacting [Zn2 Cp*2 ] with [FeCp2 ][BAr4 (F) ] in the presence of ZnMe2 . In the presence of suitable ligands, the high reactivity of 1 enables the controlled abstraction of single Zn units, providing access to the lower-nuclearity clusters \[Zn9 ](Cp*)6 \ (2) and \[Zn8 ](Cp*)5 ((t) BuNC)3 \(+) (3). According to DFT calculations, 1 and 2 can be described as closed-shell species that are electron-deficient in terms of the Wade-Mingos rules because the apical ZnCp* units that constitute the cluster cage do not have three, but only one, frontier orbitals available for cluster bonding. Zinc behaves flexibly in building the skeletal metal-metal bonds, sometimes providing one major frontier orbital (like Group 11 metals) and sometimes providing three frontier orbitals (like Group 13 elements)
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https://hal-univ-rennes1.archives-ouvertes.fr/hal-01274115
Contributor : Laurent Jonchère <>
Submitted on : Monday, February 15, 2016 - 2:07:19 PM
Last modification on : Friday, July 10, 2020 - 4:21:56 PM

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Hung Banh, Katharina Dilchert, Christine Schulz, Christian Gemel, Rüdiger W. Seidel, et al.. Atom-Precise Organometallic Zinc Clusters. Angewandte Chemie International Edition, Wiley-VCH Verlag, 2016, 55 (10), pp.3285-3289. ⟨10.1002/anie.201510762⟩. ⟨hal-01274115⟩

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