Tuning Reactivity of Platinum(II) Complexes

CHAPTER 4.
Substitution of Aqua Ligands in Pyrazine-Bridged Pt(II) Dinuclear Complexes:
Influence of the Ancillary Substituents. ................................................................................... 1
4.0 Abstract ............................................................................................................................................................... 1
4.1 Introduction ...................................................................................................................................................... 2
4.2 Experimental .................................................................................................................................................... 4
4.2.1 Chemicals and Reagents .............................................................................................................. 4
4.2.2 Synthesis of compounds .............................................................................................................. 5
4.2.3 Preparation of platinum complexes ....................................................................................... 5
4.2.4 Preparation of the dinuclear Pt(II) diaqua aqueous complexes .............................. 7
4.2.5 Instrumentation and Physical measurements .................................................................. 7
4.2.6 Computational details ................................................................................................................... 8
4.2.7 Determination of pKa values of the diaqua complexes .................................................. 9
4.2.8 Kinetic measurements .................................................................................................................. 9
4.3 Results .................................................................................................................................................................. 9
4.3.1 DFT calculated Optimized Structures ................................................................................ 10
4.3.2 Acid-base equilibria of the diaqua complexes ............................................................... 13
4.3.3 Kinetic studies on substitution reactions of the diaqua complexes .................... 16
4.3.4 Kinetics with NMR ....................................................................................................................... 22
4.4.5 Thermodynamic Parameters .................................................................................................. 25
4.5 Discussion ....................................................................................................................................................... 29
4.6 Conclusion ....................................................................................................................................................... 34
References ........................................................................................................................................................ 36
Appendix 4……………………………………………………………………………………………………… 40
Chapter 5.
Substitution Reactions in Dinuclear Platinum(II) Complexes: an Evaluation of the
influence of the diazine-bridge on reactivity ......................................................................... 1
5.0 Abstract ............................................................................................................................................................... 1
5.1 Introduction ...................................................................................................................................................... 2
5.2 Experimental ................................................................................................................................ 4
iv