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Molecular and Electronic Structures of Homoleptic Nickel and Cobalt Complexes with Non‐Innocent Bulky Diimine Ligands Derived from Fluorinated 1,4‐Diaza‐1,3‐butadiene (DAD) and Bis(arylimino)acenaphthene (BIAN)
Author(s) -
Khusniyarov Marat M.,
Harms Klaus,
Burghaus Olaf,
Sundermeyer Jörg
Publication year - 2006
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.200600236
Subject(s) - chemistry , acenaphthene , diimine , homoleptic , cobalt , crystallography , electron paramagnetic resonance , ligand (biochemistry) , nickel , homo/lumo , metal , stereochemistry , medicinal chemistry , photochemistry , inorganic chemistry , molecule , organic chemistry , catalysis , biochemistry , physics , receptor , nuclear magnetic resonance , anthracene
Abstract The diimine complexes with bulky fluorinated N ‐substituents [Ni II ( F DAD) 2 ] 1 and [Co II ( F DAD) 2 ] 2 [ F DAD = N , N′ ‐bis(pentafluorophenyl)‐2,3‐dimethyl‐1,4‐diaza‐1,3‐butadiene]as well as diimine complexes with extended π system [Ni II ( F BIAN) 2 ] 3 and [Co I ( F BIAN) 3 ] 4 ( F BIAN = bis[ N ‐{3,5‐bis(trifluoromethyl)phenyl}imino]acenaphthene) were synthesized. Compound 4 represents the first complex with three bis(imino)acenaphthene ligands synthesized so far. The molecular structures of the complexes 1 – 4 were determined by X‐ray crystallography at 193 K. Complexes 1 , 2 and 3 comprise the divalent metal ions with pairs of radical monoanionic ligands, whereas 4 is best described as a cobalt(I) complex with two neutral ( F BIAN) 0 and one ( F BIAN) 1– ligand in the radical monoanionic form. The electronic structures of the paramagnetic cobalt complexes 2 and 4 were investigated by SQUID measurements and X‐band EPR spectroscopy. Both complexes possess a doublet ground state, with electron density located mostly in the metal d‐orbitals. The doublet–quartet energy gap for 4 was established to be 159 cm –1 . (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)