Substitution behaviour of novel dinuclear Pt(II) complexes with bio-relevant nucleophiles

Dalton Trans. 2012 Jan 21;41(3):876-84. doi: 10.1039/c1dt11313e. Epub 2011 Nov 8.

Abstract

The novel dinuclear Pt(II) complexes [{trans-Pt(NH(3))(2)Cl}(2)(μ-pyrazine)](ClO(4))(2) (Pt1), [{trans-Pt(NH(3))(2)Cl}(2)(μ-4,4'-bipyridyl)](ClO(4))(2)·DMF (Pt2), and [{trans-Pt(NH(3))(2)Cl}(2)(μ-1,2-bis(4-pyridyl)ethane)](ClO(4))(2) (Pt3), were synthesized. Acid-base titrations, and temperature and concentration dependent kinetic measurements of the reactions with biologically relevant ligands such as thiourea (Tu), glutathione (GSH) and guanosine-5'-monophosphate (5'-GMP) were studied at pH 2.5 and 7.2. The reactions were followed under pseudo-first-order conditions by stopped-flow and UV-vis spectrophotometry. (1)H NMR spectroscopy was used to follow the substitution of chloride in the complex [{trans-Pt(NH(3))(2)Cl}(2)(μ-4,4'-bipyridyl)](ClO(4))(2)·DMF by guanosine-5'-monophosphate (5'-GMP) under second-order conditions. The results indicate that the bridging ligand has an influence on the reactivity of the complexes towards nucleophiles. The order of reactivity of the investigated complexes is Pt1 > Pt2 > Pt3.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Guanosine Monophosphate / chemistry
  • Magnetic Resonance Spectroscopy
  • Molecular Structure
  • Organoplatinum Compounds / chemistry*
  • Platinum / chemistry*
  • Spectrophotometry, Ultraviolet

Substances

  • Organoplatinum Compounds
  • Platinum
  • Guanosine Monophosphate