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DISPLACEMENT BY CHLORIDE OF PYRIDINE-2-CARBOXYLATE FROM DICHLORO(PYRIDINE-2-CARBOXYLATO)GOLD(III) IN ACIDIC SOLUTION; THE POSITION OF RING OPENING

DOI: 10.1039/DT9840001641

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 1641 - 1646 (1984)

Update date:2022-08-17

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Authors:

Annibale, GiulianoAnnibale, Giuliano

Canovese, LucianoCanovese, Luciano

Cattalini, LucioCattalini, Lucio

Marangoni, GiampaoloMarangoni, Giampaolo

Michelon, GianniMichelon, Gianni

Tobe, Martin L.Tobe, Martin L.

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Article abstract of DOI:10.1039/DT9840001641

The kinetics of the reaction + 2Cl- <*> - + +HN-OH (where N-O = pyridine-2-carboxylate) have been studied at 25 deg C in methanol-water (95:5,v/v).In the presence of excess of chloride, the reaction involves a fast and reversible ring opening with Au-N bond breaking (K1 = 3.16 dm3 mol-1) and a reversible protonation of the free nitrogen (K2 = 640 dm3 mol-1, corresponding to a pKa of 2.80) followed by a typical associatively activated displacement of the O-bonded ligand by chloride, with the usual rate law, kobs. = k1 + k2-> where k1 (the solvolytic rate constant) = 1.9 <*> 1E-4 s-1 and k2 = 4.54 <*> 1E-2 dm3 mol-1 s-1.In the absence of chloride a solvolytic ring opening can be observed but the reaction stops before the monodentate ligand is displaced.

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Product name:tetrachlorogold(1-)

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