[2.2]Paracyclophanes with N‐Heterocycles as Ligands for Mono‐ and Dinuclear Ruthenium(II) Complexes

[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.