Tuning Reactivity of Platinum(II) Complexes

Table of Contents-6
List of Figures ..................................................................................................................................... ii
Chapter 6 ............................................................................................................................................. 1
Tuning Reactivity of Platinum(II) Complexes with Parametalated Pyridine Spacer
Groups: A kinetic and Mechanistic Study ................................................................................... 1
6.0 Abstract .......................................................................................................................................... 1
6.1 Introduction ................................................................................................................................................. 2
6.2 Experimental ............................................................................................................................................... 4
6.2.1 Materials .................................................................................................................................................... 4
6.2.2 Instruments ............................................................................................................................................. 5
6.2.3 Preparation of 4,4’–dipyridylmonosulphide Ligand (dps) ............................................... 5
6.2.4 Synthesis of Pt(II) Complexes ......................................................................................................... 6
6.2.5 Preparation of the Dinuclear Pt(II) Diaqua Complexes ...................................................... 7
6.2.6 Preparation of Kinetic Solutions .................................................................................................... 7
6.2.7 Spectrophotometric pKa Titrations .............................................................................................. 7
6.2.8 Computational Details ........................................................................................................................ 8
6.2.9 Kinetic Measurements ........................................................................................................................ 8
6.3 Results ............................................................................................................................................................ 9
6.3.1 Synthesis and Characterization of Compounds Pt1, Pt2 and Pt3 .................................. 9
6.3.2 Acidity of the Coordinated Aqua Ligands .................................................................................. 9
6.3.4 Computation Calculations .............................................................................................................. 11
6.3.5 Kinetic Measurements ..................................................................................................................... 15
6.3.6 Activation Parameters ..................................................................................................................... 23
6.4 Discussion .................................................................................................................................................. 24
6.4.1 pKa Determination for the Diaqua Complexes ..................................................................... 24
6.4.2 Ligand Substitution ........................................................................................................................... 26
6.5 Conclusion ................................................................................................................................................. 29
References .........................................................................................................................................30
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