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Macrocyclic Triruthenium Complexes Having Electronically Coupled Mixed‐Valent States
Author(s) -
Fink Daniel,
Bodensteiner Michael,
Linseis Michael,
Winter Rainer F.
Publication year - 2018
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.201705143
Subject(s) - delocalized electron , chemistry , electrochemistry , valence (chemistry) , molecule , crystallography , mass spectrometry , electron delocalization , nuclear magnetic resonance spectroscopy , stereochemistry , organic chemistry , electrode , chromatography
5‐Ethynyl‐2‐furancarboxylic acid and 3‐ethynylbenzoic acid self‐assemble with [HRu(CO)Cl(P i Pr 3 ) 2 ] to form macrocyclic C 3 ‐symmetric triangular triruthenium alkenyl complexes [{Ru(CO)(P i Pr 3 ) 2 (CH=CHArCOO)} 3 ] (Ar=C 6 H 4 : 1‐B , Ar=C 4 H 2 O: 1‐F ), which were characterized by multinuclear NMR spectroscopy, high‐resolution ESI mass spectrometry, and, in the case of 1‐B , by X‐ray crystallography. Electrochemical studies indicate that the macrocycles are oxidized in three consecutive one‐electron steps. The mixed‐valent states obtained by electrochemical or chemical oxidation show signs of valence delocalization, which makes these complexes rare examples of molecule‐based conductive loops with through‐bond charge delocalization.