Trigonal Planar Iron(II) and Cobalt(II) Complexes Containing [RS(NtBu)3]n- (R = NtBu, n = 2; CH2PPh2, n = 1) as Acute Bite-Angle Chelating Ligands: Soft P Donor Proves Beneficial to Magnetic Co Species.

We prepared four new complexes, 4a,b and 5a,b, from polyimido sulfur-centered ligands with FeII and CoII amides. Their molecular structures were elucidated by single-crystal X-ray diffraction. Cobalt magnetic investigations and multiconfigurational calculations provided insight into magneto-structural correlations between the acute N,N' chelating bite angle and P-side arm donation. The deviation from an ideal trigonal planar geometry and the magnetic performance correlated in an unprecedented manor. Mononuclear cobalt species 4b and 5b showed slow magnetic relaxation under a small applied dc field with energy barriers of up to 33.0 and 21.9 cm-1, respectively. Although they possess some of the largest zero-field splitting parameters among three-coordinate cobalt single-ion magnets, both theory and experiment suggest that the high rhombicity (E/D) hampers large effective energy barriers to spin reversal at zero field from being obtained.