Spin-States of Diastereomeric Iron(II) Complexes of
2,6-Bis(thiazolin-2-yl)pyridine (ThioPyBox) Ligands and a Comparison
with the Corresponding PyBox Derivatives
posted on 2021-09-02, 13:47authored byNamrah Shahid, Kay E. Burrows, Mark J. Howard, Christopher M. Pask, Oscar Cespedes, Patrick C. McGowan, Malcolm A. Halcrow
This report investigates homoleptic iron(II) complexes of thiazolinyl
analogues of chiral PyBox tridentate ligands: 2,6-bis(4-phenyl-4,5-dihydrothiazol-2-yl)pyridine (L1Ph), 2,6-bis(4-isopropyl-4,5-dihydrothiazol-2-yl)pyridine
(L1iPr), and 2,6-bis(4-tert-butyl-4,5-dihydrothiazol-2-yl)pyridine
(L1t-Bu). Crystallographic
data imply the larger and more flexible thiazolinyl rings reduce steric
clashes between the R substituents in homochiral [Fe((R)-L1R)2]2+ or [Fe((S)-L1R)2]2+ (R = Ph, iPr, or t-Bu), compared
to their PyBox (L2R) analogues. Conversely,
the larger heterocyclic S atoms are in close contact with the R substituents
in heterochiral [Fe((R)-L1Ph)((S)-L1Ph)]2+, giving it a more sterically hindered ligand environment than that
in [Fe((R)-L2Ph)((S)-L2Ph)]2+ (L2Ph = 2,6-bis(4-phenyl-4,5-dihydrooxazol-2-yl)pyridine).
Preformed [Fe((R)-L1Ph)((S)-L1Ph)]2+ and [Fe((R)-L1iPr)((S)-L1iPr)]2+ do not racemize by ligand redistribution in CD3CN solution, but homochiral [Fe(L1iPr)2]2+ and [Fe(L1t-Bu)2]2+ both
undergo partial ligand displacement in that solvent. Homochiral [Fe(L1Ph)2]2+ and [Fe(L1iPr)2]2+ exhibit spin-crossover equilibria in CD3CN, centered
at 344 ± 6 K and 277 ± 1 K respectively, while their heterochiral
congeners are essentially low-spin within the liquid range of the
solvent. These data imply that the diastereomers of [Fe(L1Ph)2]2+ and [Fe(L1iPr)2]2+ show
a greater difference in their spin-state behaviors than was previous
found for [Fe(L2Ph)2]2+. Gas-phase DFT calculations (B86PW91/def2-SVP) of the [Fe(L1R)2]2+ and [Fe(L2R)2]2+ complexes reproduce
most of the observed trends, but they overstabilize the high-spin
state of SCO-active [Fe(L1iPr)2]2+ by ca. 1.5 kcal mol–1. This might reflect the influence of intramolecular dispersion interactions
on the spin states of these compounds. Attempts to model this with
the dispersion-corrected functionals B97-D2 or PBE-D3 were less successful
than our original protocol, confirming that the spin states of sterically
hindered molecules are a challenging computational problem.