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DOI: 10.1039/A701395G (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 2587-2596

Gold(III) and palladium(II) complexes of glycylglycyl-L-histidine: crystal structures of [AuIII(Gly-Gly-L-His-H-2)]Cl ·H2O and [PdII(Gly-Gly-L-His-H-2)] ·1.5H2O and HisεNH deprotonation

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Sabine L. Best, Tapan K. Chattopadhyay, Milos I. Djuran, Rex A. Palmer, Peter J. Sadler, Imre Sóvágó and Katalin Varnagy

Abstract

Proton NMR studies show that [AuCl4]- reacts slowly with glycylglycyl-L-histidine (Gly-Gly-L-His) (t½ = 9.3 h at 310 K and pH* 2) in D2O at pH* (meter reading) values as low as 1.5 to form the stable complex [AuIII(Gly-Gly-L-His-H-2)]Cl ·H2O 1 via one intermediate. Complex 1 is shown by X-ray crystallography to be square-planar with gold bound to the terminal NH2 [Au–N 2.049(10) Å], two deprotonated amide nitrogens [Au–N- 1.941(9), 2.006(10) Å] and HisδN [Au–N 2.038(9) Å] giving one six-membered and two five-membered chelate rings. At pH* 7 the reaction of [AuCl4]- with Gly-Gly-L-His follows a different course, apparently involving the formation of AuIII cross-linked polymers. The anion [PdCl4]2- reacts rapidly with Gly-Gly-L-His also at pH* 2, and forms a similar square-planar complex [PdII(Gly-Gly-L-His-H-2)] ·1.5H2O 2 involving the terminal NH2 [Pd–N 2.058(7) Å], two deprotonated amide nitrogens [Pd–N- 1.943(7), 1.983(6) Å] and HisδN [Pd–N 2.016(6) Å]. By potentiometry, pKa values of 2.58 (CO2H), 8.63 (HisεNH, ‘pyrrole nitrogen’) and 11.50 (co-ordinated NH2) for 1 and 11.30 (HisεNH) for 2 were determined and confirmed by 1H NMR spectroscopy.

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