PICKET FENCE PORPHYRINS

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A porphyrin with a protective enclosure for binding oxygen at one side of the ring that is used to mimic the dioxygen binding properties of the heme group (heme protein active site model) First synthesized by James P. Collman and his co-workers. First porphyrin to be synthesized - meso tetra (,,,-opivalaamidophenyl porphyrin)

pivalamide

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Concept Favour 5- coordination Prevent bimolecular reactions (irreversible oxidation)

STRUCTURAL FEATURES

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SYNTHE SIS

FeBr2, Cr(acac)2

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128 - Meso-tetra(o-nitrophenylporphyrin) 129 Meso tetra(o-aminophenylporphyrin) 130 ,,,-Tetrapivaloylporphyrin 131 Fe(II) Picket fence porphyrin

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B 1-MeIm 1-n-BuIm 1-tritylIm 4-tBuIm 1-MeIm 1-n-BuIm 1-MeIm

1-MeIm n-BuIm 1-tritylIm 4-tBuIm O2 O2 CO

TAILED PICKET FENCE PORPHYRINS 6-Coordination of PFP unavoidable in solutions even in

presence of sterically hindered bases Enables study of reactions with O2 or CO in solutions also. Enforces 5-coordination while retaining the ability of reversible oxidation. Base is covalently attached to o-phenyl position of TPP. Click to edit Master subtitle style

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STUDIES on cooperative oxygen binding of hemoglobin Studied by IR(O2), Mossabauer Spectroscopy,

Magnetic circular dichroism Spectroscopy, Magnetic properties. Existence of equilibrium. O2 binds in end-on angular fashion. Suggestive of multiple bond character in Fe-O bond as suggested by Pauling. Fe-O-O angle 136, O-O distance 1.24 Diamagnetic similar to HbO2 and MbO2 Similar values of oxygen affinity, H and S for oxygen binding.

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Stability of MbO2 and HbO2 complexes Effect of Dielectric constant.-Contrasting Behaviour

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Perutz Mechanism Modelling the T and R state

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STUDIES on CARBON MONOXIDE binding TO IRON PORPHYRINS Studied by interchange reactions in solidgas state and in solutions CO is bound linearly to Fe atom, Fe-C-O angle 180 Model complexes display much higher affinity than natural iron porphyrins. Role of distal His residues in natural heme proteins Click to edit Master subtitle style

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OTHER TYPES OF MODEL PICKET FENCE PORPHYRINS

Ferrocene containing picket porphyrins used to investigate photoinduced electron transfer processes and to mimic photosynthesis active sites. TPP ring with covalently attached tetrapyridine as a model for Cu/Fe binding site Click to edit Master subtitle style of cytochrome oxidase

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PICKET FENCE PORPHYRINS FOR ENATIOSELECTIVE SYNTHESIS Based on the idea that cytochrome P450 catalyses oxygenation reactions.
Hydroperoxides, Peroxy acids, PhIO can be used with metalloporphyrin enzyme mimics to catalyse O2 transfer

Epoxidation

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Aziridination

C-H Bond Functionalization

1. 2. 3.

Hydroxylation Amination Sulfoxidation

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THANK YOU

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