(Cryptand-222)potassium(+) (hydrogensulfido)[5,10,15,20-tetrakis(2-pivalamidophenyl)porphyrinato]ferrate(II)

Abstract

As part of a systematic investigation for a number of FeII porphyrin complexes used as biomimetic models for cytochrome P450, crystals of the title compound, [K(C18H36N2O6)][FeII(C64H64N8O4)(HS)], were prepared. The compound exhibits a non-planar conformation with major ruffling and saddling distortions. The average equatorial iron–pyrrole N atom [Fe—Np = 2.102 (2) Å] bond length and the distance between the FeII atom and the 24-atom core of the porphyrin ring (Fe—PC= 0.558 Å) are typical for high-spin iron(II) penta­coordinate porphyrinates. One of the tert-butyl groups in the structure is disordered over two sets with occupancies of 0.84 and 0.16.

Spectroscopic investigations into the binding of hydrogen sulfide to synthetic picket-fence porphyrins

“…38 Upon treatment of 1 with NBu 4 SH, the magnetic susceptibility changes to µ eff = 5.0µ B , supporting the formation of a high-spin (S = 2) Fe II complex, matching previously reported Fe-SH bound structures. 53,57,58 Taken together, the NMR data supports the reaction sequence in which HS − initially reduces Fe III to Fe II , after which an additional equivalent of HS − can bind to the metal center forming a ferrous hydrosulfide product.…”

Diaqua[5,10,15,20-tetrakis(4-chlorophenyl)porphyrinato-κ4N]iron(III) trifluoromethanesulfonate–4-hydroxy-3-methoxybenzaldehyde–water (1/1/2)

“…For the synthesis, see: Gismelseed et al (1990). For related structures, see: Gismelseed et al (1990); Scheidt et al (1979); Scheidt & Reed (1981); Scheidt & Finnegan (1989); Dhifet et al (2009); Xu et al (2011); Nasri et al (1990); Cheng et al (1994). For a description of the Cambridge Structural Database, see: Allen (2002).…”

“…Generally, the spin-state of the Fe(III) porphyrins depends on the value of the Fe-Np bond length. Thus, for the highspin state (S = 5/2) species, the Fe-Np distance values are large i.e, for the [Fe III (TPP)Cl] complex, Fe-Np = 2.070 9Å (Scheidt & Finnegan, 1989) and 2.125 (2) Å for the [Fe III (TpivPP)(η 2 -O 2 CO)]species (Dhifet et al, 2009). For lowspin state (S = 1/2), the Fe-Np bond length is smaller than those of high-spin Fe(III) porphyrins, i.e, for the [Fe III (TpivPP)(NO 2 ) 2 ]species, the Fe-Np distance is 1.992 (1) Å (Nasri et al, 1990).…”

Synthesis and Crystal Structure Determination of [H2‐cryptand 222](Br3)2: A Unique Tribromide Catalyst for the Catalytic Chemoselective N‐Boc Protection of Amines

“…Crown ether moieties are popular host compounds in host-guest chemistry and these ligands have shown a remarkable ability to form strong complexes with organic and inorganic cations [1][2][3] or anions, 4,5 selectively. Among the crown ethers, cryptand 222, a macrobicyclic compound, has been used in a variety of applications including the formation of a conductometric mercury [II] sensor based on poly aniline, 6 the encapsulation of alkali metals, especially K + , [7][8][9] use as an acceptor ligand for the formation of complexes containing 7,7,8,8-tetracyanoquinodimethane (TCNQ), 10 extraction of uranium(VI), 11 exchanging the cations of micas 12 and extraction of copper(II) with erythrosine B. 13 Organic tribromide reagents (OTBs) are preferable as oxidants to molecular bromine, owing to the hazards associated with elemental bromine.…”