Diane Dickie - Steric and Electronic Control of the Spin State in Three-Fold Symmetric, Four-Coordinate Iron(II) Complexes.

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      Lin, Hsiu-Jung, Siretanu, Diana, Dickie, Diane A., Subedi,   Deepak, Scepaniak, Jeremiah J., Mitcov, Dmitri, Clerac, Rodolphe,   Smith, Jeremy M. Journal of the American Chemical   Society 136 (38) 13326-13332

      Abstract: The 3-fold sym., four-coordinate   Fe(II) phosphoraminimato complexes PhB(MesIm)3Fe-N=PRR'R''   (PRR'R'' = PMePh2, PMe2Ph, PMe3, and PPr3) undergo a thermally   induced S = 0 to S = 2 spin-crossover in fluid soln. Smaller   phosphoraminimato ligands stabilize the low-spin state, and an   excellent correlation is obsd. between the characteristic temp.   of the spin-crossover (T1/2) and the Tolman cone angle (θ).   Complexes with para-substituted triarylphosphoraminimato ligands   (p-XC6H4)3P=N- (X = H, Me and OMe) also undergo spin-crossover in   soln. 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 Fe(II)   complexes. [on SciFinder(R)]

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