Redox Potential-Structure Relationships in Metal Complexes. Part 3. The Electrochemical Activation of Co-ordinated Hydrazido(2-)-ligands

DOI: 10.1039/DT9810000419

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 419 - 424 (1981)

Update date:2022-08-05

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Authors:

Crichton, Brian A. L.

Dilworth, Jonathan R.

Pickett, Christopher J.

Chatt, Joseph

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Article abstract of DOI:10.1039/DT9810000419

The complexes ⁺, R,R' = alkyl or aryl group, undergo two successive reversible one-electron reductions in non-aqueous electrolytes at platinum or vitreous carbon electrodes.The initial electron-transfer product ⁰ disproportionates to ⁺ and to the product of the second electron transfer, ^-.Two-electron reduction of the cation leads to electroactivation of the N2RR' ligand towards attack by electrophiles and reduction/protonation is shown to liberate the free hydrazine NH2NMe(Ph), in ca. 57percent yield.A plausible mechanism for this electroactivation is discussed, and from studies of related complexes, it is suggested that the redox orbitals of the ⁺ complex are associated with the Mo=N-N function.

Full text of DOI:10.1039/DT9810000419

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