vic-Dioximate Complexes of Silver(III)

Document Type

Article

Date of Original Version

9-1-1989

Abstract

Bis chelate complexes of trivalent silver with several vic-dioximate ligands [dimethylglyoximate (dmg), diphenylglyoximate (dpg), cyclohexane- 1,2-dione dioximate (chdd)] have been prepared by direct mixing of Ag(OH)4-and the ligands in alkaline solutions. These complexes are intensely colored with two ligand-to-metal charge-transfer bands at 440–470 and 556–586 nm. They undergo internal redox within several minutes with the order of stability chdd > dmg > dpg. They appear to gain maximum stability by attaining a pseudomacrocyclic structure via outside protonation. The dmg complex has an overall formation constant of 1.6 X 108M-2 at 10 °C and in 1.2 M NaOH. Formation and decomposition kinetics have been studied for the dmg complex and are interpreted in terms of stepwise chelation followed by intramolecular electron transfer in the bis and (less stable) mono complexes as well as destabilization of the +3 oxidation state by axial attack of a third ligand. © 1989, American Chemical Society. All rights reserved.

Publication Title, e.g., Journal

Inorganic Chemistry

Volume

28

Issue

19

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