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

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• 作者：Hsiu-Jung Lin ; Diana Siretanu ; Diane A. Dickie ; Deepak Subedi ; Jeremiah J. Scepaniak ; Dmitri Mitcov ; Rodolphe Cl茅rac ; Jeremy M. Smith
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：September 24, 2014
• 年：2014
• 卷：136
• 期：38
• 页码：13326-13332
• 全文大小：378K
• ISSN：1520-5126

文摘

The three-fold symmetric, four-coordinate iron(II) phosphoraminimato complexes PhB(MesIm)₃Fe鈥揘鈺怭RR鈥睷鈥?(PRR鈥睷鈥?= PMePh₂, PMe₂Ph, PMe₃, and PⁿPr₃) undergo a thermally induced S = 0 to S = 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 (T_1/2) and the Tolman cone angle (胃). Complexes with para-substituted triaryl phosphoraminimato ligands (p-XC₆H₄)₃P鈺怤^{鈥?/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.}