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The porphyrin handbook - Kadish K.M.

Kadish K.M. The porphyrin handbook - Academic press, 2000. - 368 p.
Download (direct link): kadishsmishgulilard2000.djvu
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MeO
20
Rh"
i
56
CO,R
(12A)
(12B)
irradiation of this mixture, the polymerization is initiated by
57 and is completed in a period of a few hours. Although the
polymerization has been claimed to be of a living character,72 the
polymer MWD, unfortunately, is much broader {Mw/Mn= 1.8-2.8) than in the
case with organo-cobalt porphyrins (7).
IV. Conclusion
Metalloporphyrins of aluminum, zinc, manganese, cobalt, and rhodium
complexes have been demonstrated to serve as excellent initiators for
controlled anionic and free-radical polymerizations. The discovery of
these metalloporphyrin-based initiators has led to significant
contributions to the progress of precision macromolecular synthesis via
living polymerization. In particular, it has been determined that
aluminum porphyrins are very unique initiators with an exceptionally wide
applicability. In the case of polymerization with metalloporphyrins, the
large, rigid macrocyclic porphyrin chelate is considered (1) to assure a
uniform reactivity of all growing polymer molecules; (2) to control the
electronic properties of central metal atoms; (3) to serve as light-
harvesting units; and (4) to provide a steric barrier around the active
site. Studies on steric control of polymerization with metalloporphyrins
is a subject worthy of further investigation.74-82

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