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Atom‐Precise Organometallic Zinc Clusters
Author(s) -
Banh Hung,
Dilchert Katharina,
Schulz Christine,
Gemel Christian,
Seidel Rüdiger W.,
Gautier Régis,
Kahlal Samia,
Saillard JeanYves,
Fischer Roland A.
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201510762
Subject(s) - atomic orbital , cluster (spacecraft) , zinc , chemistry , main group element , group (periodic table) , crystallography , reactivity (psychology) , atom (system on chip) , metal , open shell , group 2 organometallic chemistry , molecular orbital , computational chemistry , transition metal , molecule , electron , physics , catalysis , organic chemistry , quantum mechanics , computer science , medicine , alternative medicine , embedded system , programming language , pathology
Abstract The bottom‐up synthesis of organometallic zinc clusters is described. The cation {[Zn 10 ](Cp*) 6 Me} + ( 1 ) is obtained by reacting [Zn 2 Cp* 2 ] with [FeCp 2 ][BAr 4 F ] in the presence of ZnMe 2 . 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 {[Zn 9 ](Cp*) 6 } ( 2 ) and {[Zn 8 ](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).