(12,17-Diethoxycarbonyl-2,3,6,7,11,18-hexamethylcorrphycenato-κ⁴N)iodoiron(III) chloroform solvate

Abstract

The title complex, (diethyl 3,4,8,15,19,20-hexamethyl-21,22,23,24-tetraazopentacyclo[16.2.1.1(2,5).1(7,11).1(14,17)]tetracosa-1(20),2(22),3,5,7,9,11,13(24),14,16,18-undecaene-9,14-dicarboxylate-kappa4N)iodoiron(III) chloroform solvate, [Fe(C32H32N4O4)I].CHCl3, shows an almost planar arrangement of the corrphycene moiety with a slightly distorted trapezoid pyramidal core; the Fe(III) atom is 0.416 (1) A from the plane of the C20N4 system. The Fe-N distances are 2.049 (3), 2.044 (3), 2.079 (3) and 2.075 (3) A. The solvated chloroform forms a C-H...O hydrogen bond [C...O 3.107 (10) A] to an adjacent carbonyl O atom. This is the first X-ray structure analysis of a corrphycenatoiron(III) derivative.

Novel Controlling Mechanism of the Oxygen Affinity in Myoglobin With Isomeric Porphyrins

“…The N(pyrrole)‐Fe bonds are not orthogonal and the two of the four N(pyrrole)‐Fe‐N(pyrrole) bond angles are 74° and 106°. The molecular structures of the iron complexes of hemiporphycene and porphycene have been also reported by Ohgo and coworkers (7,8). The overall structures of these iron complexes resemble that of iron porphyrin.…”

“…Although their metallo core significantly deviates from square, these macrocycles are capable of combining iron atoms. Figure 2 illustrates the molecular structure of ferric iron corrphycene with iodine as the axial ligand (7). The iron atom is not in the middle of the core but slightly deviates to the narrower side of the trapezoid.…”

“…The crystal structure of the iron complexes of porphyrin isomers was determined as described previously (7–9). The oxygen affinity of the developed Mb was determined with the automatic recording apparatus (10).…”

14 Iron, cobalt and nickel

“…Chloro(3,6,13,16-tetraethyl-2,7,12,17-tetramethylporphycenato)iron() has distorted square-pyramidal co-ordination of iron, 98 as do iodo(12,17-diethoxycarbonyl-2,3,6, 7,11,18-hexamethylporphycenato)iron() 99 and [Fe(TDFPP)(OCH 3 )], 100 whereas [Fe(TPriP)(thf ) 2 ]ClO 4 has six-co-ordination. 101 The S = 3/2 compound [FeCl-(OETPP)] has square pyramidal co-ordination of iron; the macrocyle is saddle-shaped with a little ruffling.…”

Significance of the Molecular Shape of Iron Corrphycene in a Protein Pocket

“…The argument comes from the characteristic molecular shape of corrphycene. According to the X-ray analyses of metallocorrphycene, the metal atom is not in the middle of the coordination core but shifted toward the bipyrrole moiety to produce the longer and shorter metal−N(pyrrole) bonds. ,− For the ferric iron complexes, the Fe−N(bipyrrole) and Fe−N(dipyrroethene) distances are 2.014−2.049 and 2.049−2.079 Å, respectively. , The inductive effect of the substituents could be transmitted more efficiently to the Fe atom through the shorter Fe−N(bipyrrole) bonds. It is also likely that the moderately bulky ethoxycarbonyl groups on the bipyrrole moiety of corrphycene B (Figure ) are under steric repulsion to constrain the macrocycle.…”