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Synthesis, Characterization, and Reactivity of a Series of Homo‐ and Hetero‐dinuclear Complexes based on an Asymmetric FloH Ligand System
Author(s) -
Battistella Beatrice,
Heims Florian,
Cula Beatrice,
Ray Kallol
Publication year - 2020
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.202000221
Subject(s) - reactivity (psychology) , chemistry , ligand (biochemistry) , intramolecular force , metalation , metal , chelation , crystallography , stereochemistry , copper , inorganic chemistry , organic chemistry , receptor , medicine , biochemistry , alternative medicine , pathology
In a previous communication we reported the site‐directed generation of a heterodinuclear Fe III Cu II complex ( 1 ) by using an asymmetric dinucleating ligand FloH. The iron(III) ion was introduced first on the preferential metal‐binding site of the ligand that led to the formation of the thermodynamically favored five‐membered chelate ring upon metal‐binding. Copper(II) was introduced in the next step. The stepwise metalation strategy reported previously has now been extended to synthesize a series of heterodinuclear Fe III M II [M = Mn ( 2 ), Fe ( 3 ), Co ( 4 ), and Ni ( 5 )] and Fe II Cu I ( 1a ) as well as the homodinuclear Cu I Cu I ( 6 ) complexes. The complexes were characterized by X‐ray crystallography (except for 1a and 6 ), and by a limited number of spectroscopic methods. Complex 1 with a labile solvent binding site at Fe III reacted with H 2 O 2 to form a transient intermediate that showed reactivity typical of metal peroxide complexes. The metal centers in the complexes 2 – 5 are coordinatively saturated, and hence they showed no reactivity with H 2 O 2 . Complex 1a reacted with O 2 via an intermolecular pathway to form a μ‐oxo bridged tetrameric complex 1b , which was structurally characterized. This is in contrast to the homodinuclear Cu I Cu I and heme Fe II Cu I cores, which prefer an intramolecular pathway for O 2 activation.