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Stack by Stack: From the Free Cyclopentadienylgermanium Cation Via Heterobimetallic Main‐Group Sandwiches to Main‐Group Sandwich Coordination Polymers
Author(s) -
Schorpp Marcel,
Krossing Ingo
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202002932
Subject(s) - cationic polymerization , chemistry , crystallography , indium , ligand (biochemistry) , group (periodic table) , stereochemistry , polymer , gallium , polymer chemistry , organic chemistry , receptor , biochemistry
Heterobimetallic cationic sandwich complexes [M(μ‐Cp)M′Cp] + of group 13 (M=Ga, In) and group 14 (M′=Ge, Sn) elements have been prepared as [WCA] − salts (WCA=Al(OR F ) 4 ; OR F =OC(CF 3 ) 3 ). Their molecular structures include free apical gallium or indium atoms. The sandwich complexes were formed in the reactions of [M(HMB)] + [WCA] − (HMB=C 6 Me 6 ) with the free metallocenes [M′Cp 2 ]. Their structures are related to known stannocene and stannocenium salts; the unprecedented germanium analogues, namely the free germanocenium cation [GeCp] + and the corresponding triple‐decker complex cation [CpGe(μ‐Cp)GeCp] + , are described herein. By variation of the reaction conditions, these sandwich complexes can be transformed into the group 13/14 mixed cationic coordination polymer [{In(HMB)(μ‐SnCp 2 )} n ][WCA] n . This polymeric chain motif was also successfully replicated by the synthesis of complexes [{Ga/In(HMB)(μ‐FeCp 2 )} n ][WCA] n containing FeCp 2 as a bridging ligand.