Bis(cyano) Iron(III) Porphyrinates: What Is the Ground State?

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• 作者：Jianfeng Li ; Bruce C. Noll ; Charles E. Schulz ; W. Robert Scheidt
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：July 6, 2015
• 年：2015
• 卷：54
• 期：13
• 页码：6472-6485
• 全文大小：723K
• ISSN：1520-510X

文摘

The synthesis of six new bis(cyano) iron(III) porphyrinate derivatives is reported. The anionic porphyrin complexes utilized tetraphenylporphyrin, tetramesitylporphyrin, and tetratolylporphyrin as the porphyrin ligand. The potassium salts of Kryptofix-222 and 18-C-6 were used as the cations. These complexes have been characterized by X-ray structure analysis, solid-state M枚ssbauer spectroscopy, and EPR spectroscopy, both in frozen CH₂Cl₂ solution and in the microcrystalline state. These data show that these anionic complexes can exist in either the (d_xz,d_yz)⁴(d_xy)¹ or the (d_xy)²(d_xz,d_yz)³ electronic configuration and some can clearly readily interconvert. This is a reflection that these two states can be very close in energy. In addition to the effects of varying the porphyrin ligand, subtle effects of the cyanide ligand environment in the solid state and in solution are sufficient to shift the balance between the two electronic states.