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C 60 3– versus C 60 4– /C 60 2– – Synthesis and Characterization of Five Salts Containing Discrete Fullerene Anions
Author(s) -
Boeddinghaus M. Bele,
Klein Wilhelm,
Wahl Bernhard,
Jakes Peter,
Eichel RüdigerA.,
Fässler Thomas F.
Publication year - 2014
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201300607
Subject(s) - fullerene , chemistry , disproportionation , crystallography , ion , electron paramagnetic resonance , rubidium , crystal structure , potassium , nuclear magnetic resonance , organic chemistry , physics , catalysis
Five new compounds, [Rb(18crown‐6)] 3 [C 60 ] ( 1 ), [Rb(18crown‐6)] 6 [C 60 ] 2 (C 3 H 7 NO) 2 (C 4 H 8 O) 2 ( 2 ), [Rb(benzo18crown‐6)] 6 [C 60 ] 2 (C 2 H 8 N 2 ) 5 ( 3 ), [Cs(benzo18crown‐6)] 3 C 60 (C 2 H 8 N 2 ) 2 ( 4 ), and [Cs 3 (benzo18crown‐6) 5 ]C 60 (C 2 H 8 N 2 ) (4.5+x) ( 5 ) were synthesized and characterized by single‐crystal X‐ray structure determination. All compounds contain discrete C 60 anions, which are ordered in 1 , 2 , and 4 , where direct cation‐anion contacts occur. The unit cells of 1 and 2 contain two independent fullerides, which coordinate to the rubidium atoms either of two or of four [Rb(18crown‐6)] units. Owing to the presence of differently coordinated fullerene units in compounds 1 and 2 , a possible disproportionation of C 60 3– into C 60 2– and C 60 4– anions is discussed. In 3 and 4 the C 60 anions are coordinated by three Rb and Cs atoms, respectively. In all compounds the average charge of the anion is –3. Magnetic data reveal a doublet spin state for 3 . The EPR spectra are discussed for compounds 3 and 5 . The role of a dynamic Jahn‐Teller distortion is discussed, and we report the first IR spectroscopic data of fullerene trianions, which have been obtained in solution.