Atom-Precise Organometallic Zinc Clusters.

Authors :: Banh H
Dilchert K
Schulz C
Gemel C
Seidel RW
Gautier R
Kahlal S
Saillard JY
Fischer RA
Source :: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2016 Mar 01; Vol. 55 (10), pp. 3285-9. Date of Electronic Publication: 2016 Feb 05.
Publication Year :: 2016
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).<br /> (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)