Iron(tetraphenylporphyrinato) chloride

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Iron(tetraphenylporphyrinato) chloride
FeTPPCl.png
Names
Other names
fecl(tpp)
Identifiers
3D model (JSmol)
ChemSpider
  • InChI=1S/C44H28N4.ClH.Fe/c1-5-13-29(14-6-1)41-33-21-23-35(45-33)42(30-15-7-2-8-16-30)37-25-27-39(47-37)44(32-19-11-4-12-20-32)40-28-26-38(48-40)43(31-17-9-3-10-18-31)36-24-22-34(41)46-36;;/h1-28H;1H;/q-2;;+3/p-1/b41-33-,41-34-,42-35-,42-37-,43-36-,43-38-,44-39-,44-40-;;
    Key: ZDYSAMCSFRQDMN-YKKPBKTHSA-M
  • c1ccc(cc1)/c/2c\3/nc(/c(c/4\n5/c(c(\c6n/c(c(\c7n(c2cc7)[Fe]5Cl)/c8ccccc8)/C=C6)/c9ccccc9)/cc4)/c1ccccc1)C=C3
Properties
C44H28ClFeN4
Molar mass 704.03 g·mol−1
Appearance dark blue solid
Density 1.318 g/cm3
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Iron(tetraporphyriinato) chloride is the coordination complex with the formula Fe(TPP)Cl where TPP is the dianion [C44H28N4]2-. The compound forms blue microcrystals that dissolve in chlorinated solvent to give brown solutions. In terms of structure, the complex is five-coordinate with idealized C4v point group symmetry.[1] It is one of more common transition metal porphyrin complexes.

Synthesis and reactions[edit]

Fe(TPP)Cl is prepared by the reaction of tetraphenylporphyrin (H2TPP) and ferrous chloride in the presence of air:

H2TPP + FeCl2 + 1/4 O2 → Fe(TPP)Cl + HCl + 1/2 H2O

The chloride can be replaced with other halides and pseudohalides. Base gives the "mu-oxo dimer":

2 Fe(TPP)Cl + 2 NaOH → [Fe(TPP)]2O + 2 NaCl + H2O

Most relevant to catalysis, the complex is easily reduced to give ferrous derivatives (L = pyridine, imidazole):

Fe(TPP)Cl + e- + 2 L → Fe(TPP)L2 + Cl

The complex is widely studied as a catalyst.[2][3]

References[edit]

  1. ^ Hunter, Seth C.; Smith, Brenda A.; Hoffmann, Christina M.; Wang, Xiaoping; Chen, Yu-Sheng; McIntyre, Garry J.; Xue, Zi-Ling (2014). "Intermolecular Interactions in Solid-State Metalloporphyrins and Their Impacts on Crystal and Molecular Structures". Inorganic Chemistry. 53 (21): 11552–11562. doi:10.1021/ic5015835. PMID 25338536.
  2. ^ Cui, Xin; Zhang, X. Peter (2012). "Iron(III)meso-Tetraphenylporphine Chloride". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rn01388. ISBN 978-0471936237.
  3. ^ Pegis, M. L.; Martin, D. J.; Wise, C. F.; Brezny, A. C.; Johnson, S. I.; Johnson, L. E.; Kumar, N.; Raugei, S.; Mayer, J. M. (2019). "Mechanism of Catalytic O2 Reduction by Iron Tetraphenylporphyrin". Journal of the American Chemical Society. 141 (20): 8315–8326. doi:10.1021/jacs.9b02640. PMC 6684231. PMID 31042028.