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[2.2]Paracyclophanes with N‐Heterocycles as Ligands for Mono‐ and Dinuclear Ruthenium(II) Complexes
Author(s) -
Braun Carolin,
Nieger Martin,
Thiel Werner R.,
Bräse Stefan
Publication year - 2017
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.201703291
Subject(s) - ruthenium , chemistry , cationic polymerization , substituent , diastereomer , derivative (finance) , cyclophane , combinatorial chemistry , stereochemistry , catalysis , crystal structure , crystallography , polymer chemistry , organic chemistry , financial economics , economics
[2.2]Paracyclophane, with its unique structure, allows the design of unusual 3D structures by functionalization of this rigid and stable hydrocarbon scaffold. Therefore different mono‐ and homodisubstituted [2.2]paracyclophanes with pyridyl, pyrimidyl and oxazolinyl substituents were developed in order to evaluate their ability as bridging ligands for two ruthenium centres. With the successfully synthesized [2.2]paracyclophane‐based N ‐donor functions, the cycloruthenation reaction using [RuCl 2 ( p ‐cymene)] 2 as precursor was explored. Compared to 2‐phenylpyridine, the [2.2]paracyclophane derivative is clearly inferior in the cycloruthenation reaction, resulting in poor yields for the neutral complexes. By addition of KPF 6 , the cationic complexes can be obtained in good yields and are formed diastereoselectively in case of a pyridyl substituent, resulting in only one diastereomer for dinuclear ruthenium complexes of bispyridyl‐substituted [2.2]paracyclophanes as bridging ligands.