Electronic, Magnetic, and Structural Characterization of the Five-Coordinate, High-Spin Iron(II) Nitrato Complex [Fe(TpivPP)(NO3)]-

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• 作者：Habib Nasri ; Mary K. Ellison ; Ben Shaevitz ; Govind P. Gupta ; and W. Robert Scheidt
• 刊名：Inorganic Chemistry
• 出版年：2006
• 出版时间：July 10, 2006
• 年：2006
• 卷：45
• 期：14
• 页码：5284 - 5290
• 全文大小：157K
• 年卷期：v.45,no.14(July 10, 2006)
• ISSN：1520-510X

文摘

The preparation and characterization of the five-coordinate iron(II) porphyrinate derivative [Fe(TpivPP)(NO₃)]^- (TpivPP= picket-fence porphyrin) is described. Structural and magnetic susceptibility data support a high-spin state (S =2) assignment for this species. The anionic axial nitrate ligand is O-bound, through a single O atom, with an Fe-Obond length of 2.069(4) Å. The planar nitrate ligand bisects a N_p-Fe-N_p angle. The average Fe-N_p bond lengthis 2.070(16) Å. The Fe atom is located 0.49 Å out of the 24-atom mean porphyrin plane toward the nitrate ligand.From solid-state Mössbauer data, the isomer shift of 0.98 mm/s at 77 K is entirely consistent with high-spin iron(II).However the quadrupole splitting of 3.59 mm/s at 77 K is unusually high for iron(II), S = 2 systems but within therange of other five-coordinate high-spin ferrous complexes with a single anionic axial ligand. Crystal data for [K(222)][Fe(TpivPP)(NO₃)]·C₆H₅Cl: a = 17.888 (5) Å, b = 21.500 (10) Å, c = 22.514 (11) Å, = 100.32 (3), monoclinic,space group P2₁/n, V = 8519 ų, Z = 4.