Cyclophane hemes

Cyclopentene-l-dithiocarboxylic acid, 2-amino-meta complexes, 2, 800 Cyclophane chlorophylls, 3, 58 Cyclophane hemes iron complexes, 4,1269 Cyclophosphazenes metal complexes, 2, 81 Cyclopropane carbonylation... 

Detailed kinetic studies of the reaction of Fe(II) in cyclophane hemes with 02 and with CO probed polarity and steric effects the effects of deformation of the porphyrin skeleton from planarity were assessed for one compound (121). Volume profiles have been established for reactions of a lacunar Fe(II) complex with CO (122 for myoglobin with 02 and with CO and for hemerythrin with 02 (123). 

Another indication of steric interference is seen in the reaction of the tetracoordinated heme cyclophane with CO in dry benzene. Under conditions (1 atm CO) where deuteroheme exists as an approximately equal mixture of the mono-CO and di-CO complexes (37), the cyclophane heme shows the distinct spectrum of the pure mono-CO complex. Thus distal-side residues in heme pockets should be capable of greatly altering ligation of CO, and probably of 02 as well. 

In order to have available an adjustable steric effect, we have prepared the anthracene heme cyclophane and the bicyclophane shown below (36). The severe interference of both cyclophane pock-... 

One of the initial examples of the strapped porphyrin approach to heme protein models was the cyclophane porphyrin 193 of Diekmann et al. . In this example steric... 

Figure 6.3. Synthesis of anthracene-heme [6,6] cyclophane and of pagoda porphyrin (240).

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