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Unusually Strong Long‐Distance Metal–Metal Coupling in Bis(ferrocene)‐Containing BOPHY: An Introduction to Organometallic BOPHYs
Author(s) -
Rhoda Hannah M.,
Chanawanno Kullapa,
King Alexander J.,
Zatsikha Yuriy V.,
Ziegler Christopher J.,
Nemykin Victor N.
Publication year - 2015
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.201504004
Subject(s) - ferrocene , metal , group 2 organometallic chemistry , coupling (piping) , chemistry , polymer chemistry , materials science , inorganic chemistry , metallurgy , organic chemistry , molecule , electrochemistry , electrode
The first organometallic BOPHY (BOPHY=bis(difluoroboron)‐1,2‐bis{(pyrrol‐2‐yl)methylene}hydrazine) containing two ferrocene substituents was prepared through a Knoevenagel condensation between tetramethyl substituted BOPHY and ferrocene carboxaldehyde. An unprecedentedly strong long‐range (≈17.2 Å) metal–metal coupling in this new complex was investigated using electrochemical, spectroelectrochemical, and chemical oxidation methods. Electrochemical data is indicative of a 200 mV separation between the first and the second ferrocene‐centered oxidation processes. Formation of the mixed‐valence states and appearance and disappearance of two NIR bands were observed during stepwise oxidation of the first organometallic BOPHY. The electronic structure and the nature of the excited states in this new chromophore were studied by DFT and TDDFT calculations.