Porphyrins

• Heterocyclic tetrapyrrolic organic molecules

• Composed of four pyrrolic units linked in a coplanar fashion by four
methene bridges that give a planar macrocyclic structure to the
porphyrin molecule
• Extended conjugated 18 π-electron system - responsible
for its aromatic behavior,
• Limited size cavity - accommodation of large metal
cations
• Due to the conjugation of π-electrons on the frontier
orbitals, porphyrins possess distinctive UV–VIS spectra
Explain
• Extensive conjugation of 18 electrons in porphyrins gives
rise to facile π→π* transitions that give rise to two
distinct bands within the visible region of electromagnetic
radiations.
• Insertion of a metal ion into the porphyrin cavity or the
protonation of the nitrogen atoms or variation of the
peripheral substituents may result in a change in the
wavelength and intensity of the absorption spectrum.
Metalloporphyrins
• Formed when the metal ions fit into the
porphyrin core
Two types (size of coordinating metal cations).
• Cationic metal size of coordinating metal is 55–80
pm - in-plane metalloporphyrins
The metal centers are situated in the plane of
porphyrin rings.
• Cationic radius is greater than 80– 90 pm - out-of-
plane or sitting-atop (SAT) metalloporphyrins
Metal atoms are located out of the porphyrin plane
Give an example of a metalloporphyrin
Metalloporphyrins in Nature
Metalloporphyrins in Nature
• The Fe2+ containing heme group , is not just the oxygen carrier
found in hemoglobin; it is a cofactor of hemeproteins including
cytochromes and peroxidases that carry out diverse biological
reactions.
• Chlorophyll, a family of green pigments that absorb sunlight, is
central to photosynthesis. It chelates a magnesium atom center.
Chlorophyll is a reduced porphyrin (chlorin) macrocycle, which
contains two π electrons less than porphyrin.
• Vitamin B12, a crucial vitamin for nervous system function. It
contains a cobalt atom in the center of the aromatic tetrapyrrole.
• Cofactor F430, a nickel-containing tetrapyrrole (Fig. 2D), is found
in methyl-coenzyme M reductase (MCR) and catalyzes the
terminal step of methanogenesis. The successful biosynthesis of
F430 was achieved recently and holds potential for industrial
metabolic bioenergetic engineering