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Reduction of tetrakis(4-N-methylpyridyl)porphinecobalt(III) by hexaammineruthenium(II). [Spectral studies of effects of pH and added ions on reduction]

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic50157a029· OSTI ID:7364396
The reduction of tetrakis(4-N-methylpyridyl)porphinecobalt(III) (Co/sup III/TMpyP) by Ru(NH/sub 3/)/sub 6//sup 2 +/ has been studied as a function of pH and added anions. In the range 2 x 10/sup -5/ < or = (H/sup +/) < or = 0.50 M, the reactions are pH independent and the catalytic effects of chloride and thiocyanate ions are quite modest; rate constants (M/sup -1/ s/sup -1/, 25/sup 0/C) in sulfonate media containing chloride and thiocyanate are given by 1.2 x 10/sup 5/ + 3.3 x 10/sup 5/(Cl/sup -/) + 6.6 x 10/sup 5/(SCN/sup -/). A more pronounced influence on rate occurs when thiocyanate or azide ions are bonded directly to the cobalt site. The rate constants for the Ru(NH/sub 3/)/sub 6//sup 2 +/ reduction of CoP(H/sub 2/O)(SCN)/sup 4 +/ is 10 times larger and that for CoP(H/sub 2/O)(N/sub 3/)/sup 4 +/ is 20 times smaller than that for CoP(H/sub 2/O)/sub 2//sup 5 +/ in a similar medium. (auth)
Research Organization:
Ithaca Coll., NY
OSTI ID:
7364396
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 15:3; ISSN INOCA
Country of Publication:
United States
Language:
English