Mechanistic studies on Hydrazido(2-)-complexes. Cleavage of the Nitrogen-Nitrogen Bond in the Reaction of (CH2)4CH2>(Ph2PCH2PPh2)2> with Acid

DOI: 10.1039/DT9890000425

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Journal of the Chemical Society, Dalton Transactions p. 425 - 430 (1989)

Update date:2022-07-31

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Authors:

Henderson, Richard A.

Leigh, G. Jeffery

Pickett, Christopher J.

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Article abstract of DOI:10.1039/DT9890000425

The kinetics of the reaction between (CH2)4CH2<*>>(dppe)2> (dppe=Ph2PCH2CH2PPh2) and BPh4 to yield NH<*>(CH2)4CH2<*> and BPh4 (RCN is the solvent; R=Me, Et, or Ph) has been studied.In general the mechanism of the reactions involves two parallel pathways.Initial rapid protonation of the hydrazido(2-)-ligand and attack of a solvent molecule at the metal yields the spectrophotometrically detected hydrazidium species, trans-(CH2)4CH2<*>>(NCR) (dppe)2>⁺.This species can either undergo slow nitrogen-nitrogen cleavage or react via an acid-catalysed pathway involving trans-(CH2)4CH2<*>>(NCR) (dppe)2>²⁺ to yield products.The factors influencing whether protonation of hydrazido(2-)-ligands results in amine formation (N-N bond cleavage) or hydrazine formation (M-N bond cleavage) are discussed.

Full text of DOI:10.1039/DT9890000425

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