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Multiferrocenyl Cobalt‐Based Sandwich Compounds
Author(s) -
Filipczyk Grzegorz,
Lehrich Steve W.,
Hildebrandt Alexander,
Rüffer Tobias,
Schaarschmidt Dieter,
Korb Marcus,
Lang Heinrich
Publication year - 2017
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201600848
Subject(s) - cyclobutadiene , chemistry , cobalt , cyclic voltammetry , metal , mass spectrometry , electronic structure , analytical chemistry (journal) , crystallography , inorganic chemistry , computational chemistry , electrochemistry , organic chemistry , molecule , electrode , chromatography
The reaction of FcC≡C–C≡CFc [Fc = Fe(η 5 ‐C 5 H 4 )(η 5 ‐C 5 H 5 )] ( 1 ) with Co(η 5 ‐C 5 H 5 )(CO) 2 ( 2 ) afforded ferrocenyl‐functionalized cyclobutadiene and cyclopentadienone cobalt(I) compounds as well as multiferrocenyl benzene derivatives. The synthesis procedures are described. Eleven products could be separated by column chromatography and were characterized by NMR, UV/Vis, and IR spectroscopy, high‐resolution ESI‐TOF mass spectrometry and elemental analysis. For five representatives, the structure in the solid state was determined by single X‐ray structure analysis. The electronic properties of the appropriate compounds were studied by using cyclic and square‐wave voltammetry. Further investigation of the interaction between Fe II /Fe III centers in the mixed‐valent species was achieved by in situ UV/Vis/NIR spectroelectrochemistry. These measurements demonstrated that weak electronic metal–metal interactions through the cobalt‐coordinated cyclobutadiene building block occur (weakly coupled class II systems according to the classification of Robin and Day), whereas the cyclopentadienone core acts as an insulator (class I), and hence only electrostatic interactions are characteristic.