Steric
and Electronic Control of the Spin State in
Three-Fold Symmetric, Four-Coordinate Iron(II) Complexes
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Abstract
The
three-fold symmetric, four-coordinate iron(II) phosphoraminimato
complexes PhB(MesIm)<sub>3</sub>Fe–NPRR′R″
(PRR′R″ = PMePh<sub>2</sub>, PMe<sub>2</sub>Ph, PMe<sub>3</sub>, and P<sup>n</sup>Pr<sub>3</sub>) undergo a thermally induced <i>S</i> = 0 to <i>S</i> = 2 spin-crossover in fluid
solution. Smaller phosphoraminimato ligands stabilize the low-spin
state, and an excellent correlation is observed between the characteristic
temperature of the spin-crossover (<i>T</i><sub>1/2</sub>) and the Tolman cone angle (θ). Complexes with <i>para</i>-substituted triaryl phosphoraminimato ligands (<i>p</i>-XC<sub>6</sub>H<sub>4</sub>)<sub>3</sub>PN<sup>–</sup> (X = H, Me and OMe) also undergo spin-crossover in solution. These
isosteric phosphoraminimato ligands reveal that the low-spin state
is stabilized by more strongly donating ligands. This control over
the spin state provides important insights for modulating the magnetic
properties of four-coordinate iron(II) complexes