Direct Incorporation of a Ferric Ion in the Porphyrinogen Core: Tetrakis(cyclohexyl)iron Porphyrinogen Anion with Different Conformers and Its Reaction with Iodine
详细信息 查看全文
- 作者：Dibyendu Bhattacharya ; Soumen Dey ; Suman Maji ; Kuntal Pal ; and Sabyasachi Sarkar
- 刊名：Inorganic Chemistry
- 出版年：2005
- 出版时间：October 31, 2005
- 年：2005
- 卷：44
- 期：22
- 页码：7699 - 7701
- 全文大小：124K
- 年卷期：v.44,no.22(October 31, 2005)
- ISSN：1520-510X
文摘
Et4N[L' 'FeIII]·3DCM (1) is directly synthesized by adding ferricchloride into a solution of a lithium salt of tetrakis(cyclohexyl)porphyrinogen (L' '). [L' ']4- is a good chelating ligand for both Fe(III) and Fe(II) ions. It is an avid proton scavenger but not areducing agent. 1 showed a magnetic moment (
eff) of 4.3 B inthe solid, which changed to 6.0 B in solution. This change inspin state is common for all iron porphrinogens. 1 showedpolymorphism, and with pyridine in the lattice, it changed to Et4N[L' 'FeIII]·DCM0.5Py1.5 (2), possessing two different conformers.Calculation of these conformers at the density functional theorylevel showed the relative energies of all d orbital changes in threeconformers, highlighting the influence of the disposition of aperipheral ligand. Iodine oxidation of 1 yielded [L' '
FeIII][I3·I2+·I3-](3) with the introduction of two C
-C bonds with concomitantreduction of Fe(III) to Fe(II). Its eff (5.4 B) in the solid changedto 4.8 B in solution, suggesting a high spin state (S = 2) forFe(II).
eff) of 4.3 B inthe solid, which changed to 6.0 B in solution. This change inspin state is common for all iron porphrinogens. 1 showedpolymorphism, and with pyridine in the lattice, it changed to Et4N[L' 'FeIII]·DCM0.5Py1.5 (2), possessing two different conformers.Calculation of these conformers at the density functional theorylevel showed the relative energies of all d orbital changes in threeconformers, highlighting the influence of the disposition of aperipheral ligand. Iodine oxidation of 1 yielded [L' 'FeIII][I3·I2+·I3-](3) with the introduction of two C-C bonds with concomitantreduction of Fe(III) to Fe(II). Its eff (5.4 B) in the solid changedto 4.8 B in solution, suggesting a high spin state (S = 2) forFe(II).