Tuning Metal–Metal Interactions through Reversible
Ligand Folding in a Series of Dinuclear Iron Complexes
Posted on 2019-08-23 - 19:35
A dinucleating
macrocyclic ligand with two redox-active, pyridyldiimine
components was shown to undergo reversible ligand folding to accommodate
various substitution patterns, metal ion spin states, and degrees
of Fe–Fe bonding within the cluster. An unfolded-ligand geometry
with a rectangular Fe2(μ-Cl)2 core and
an Fe–Fe distance of 3.3262(5) Å served as a direct precursor
to two different folded-ligand complexes. Chemical reduction in the
presence of PPh3 resulted in a diamagnetic, folded ligand
complex with an Fe–Fe bonding interaction (dFe–Fe = 2.7096(17) Å) between two intermediate
spin (SFe = 1) Fe(II) centers. Ligand
folding was also induced through anion exchange on the unfolded-ligand
species, producing a complex with three PhS– ligands
and a temperature-dependent Fe–Fe distance. In this latter
example, the weak ligand field of the thiolate ligands led to a product
with weakly coupled, high-spin Fe(II) ions (SFe = 2; J = −50.1 cm–1) that form a bonding interaction in the ground state and a nonbonding
interaction in the excited state(s), as determined by SQUID magnetometry
and variable temperature crystallography. Finally, both folded-ligand
complexes were shown to reform an unfolded-ligand geometry through
convergent syntheses of a complex with an Fe–Fe bonded Fe2(μ-SPh)2 core (dFe–Fe = 2.7320(11) Å). Experimentally validated DFT calculations
were used to investigate the electronic structures of all species
as a way to understand the origin of Fe–Fe bonding interactions,
the extent of ligand reduction, and the nature of the spin systems
that result from multiple, weakly interacting spin centers.
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Zhang, Shaoguang; Wang, Qiuran; Thierer, Laura M.; Weberg, Alexander B.; Gau, Michael R.; Carroll, Patrick J.; et al. (2019). Tuning Metal–Metal Interactions through Reversible
Ligand Folding in a Series of Dinuclear Iron Complexes. ACS Publications. Collection. https://doi.org/10.1021/acs.inorgchem.9b01673
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AUTHORS (7)
SZ
Shaoguang Zhang
QW
Qiuran Wang
LT
Laura M. Thierer
AW
Alexander B. Weberg
MG
Michael R. Gau
PC
Patrick J. Carroll
NT
Neil C. Tomson