Influence of the bridging ligand on the substitution behaviour of dinuclear Pt(II) complexes. An experimental and theoretical approach.
A series of dinuclear Pt(II) complexes of the type [Pt2(N,N,N',N'-tetrakis(2-pyridylmethyl)diamine(H2O)2]4+ were synthesized. Acid-base titrations, and concentration and temperature dependent stopped-flow measurements of the reaction with chloride were performed to study the thermodynamic and kinetic behaviour of the dinuclear bridged complexes. The results indicate that there is a clear interaction between the two Pt(II) centres, which becomes weaker as the aliphatic chain increases in length. From a certain chain length onwards, the Pt(II) centres become independent of each other and exhibit identical thermodynamic and kinetic properties. The experimental results are discussed in reference to structures obtained by DFT (BP86/LACVP*) calculations.
Ertürk
Hakan
H
Institute for Inorganic Chemistry, University of Erlangen-Nürnberg, Egerlandstr. 1, 91058, Erlangen, Germany.
Hofmann
Andreas
A
Puchta
Ralph
R
van Eldik
Rudi
R
D002712:Chlorides / Q000737:chemistry; D007202:Indicators and Reagents; D007700:Kinetics; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D009944:Organoplatinum Compounds / Q000138:chemical synthesis*; D011789:Quantum Theory; D012996:Solutions; D013329:Structure-Activity Relationship; D013696:Temperature; D013816:Thermodynamics
D002712:Chlorides; D007202:Indicators and Reagents; D008024:Ligands; D009944:Organoplatinum Compounds; D012996:Solutions