Title

Substitution reactions of a water-soluble metalloporphyrin with azide and 1,1,3,3-tetramethyl-2-thiourea

Document Type

Article

Publication Date

1-1-1978

Abstract

The substitution reactions of tetrakis-(4-N-methylpyridyl)porphinecobalt (III) (Co TMpyP) with azide and with 1,1,3,3-tetramethyl-2-thiourea (TMTU) have been studied as a function of pH at 25° and an ionic strength of 0.5 M. The mechanistic pathway proposed for thiocyanate [1] and pyridine [2] is applicable to these ligands as well once allowance is made for two attacking forms of azide, N and HN . A TMTU axial substituent has about the same influence on the rate of further ligand substitution as does SCN and a much larger influence than does azide. Similar behavior between bound SCN and bound TMTU is also shown in electron-transfer reactions with Ru(NH ) - Whereas both sulfur-containing ligands enhance the rate relative to the diaquo complex, the azide complex undergoes reduction an order of magnitude more slowly than does the diaquo complex. © 1978. III - - - 2+ 3 3 3 6

Publication Name

Bioinorganic Chemistry

Volume Number

8

First Page

33

Last Page

44

Issue Number

1

DOI

10.1016/S0006-3061(00)80003-4

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