Maidich, Luca (2014) Synthesis and reactivity of cycloplatinated rollover complexes, an experimental and theoretical approach. Doctoral Thesis.
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Cyclometalation reactions constitute one of the evergreen fields in synthetic chemistry because of the variety of applications, from substrate functionalization to catalyst production and model for C-H activation. A variation on this theme is rollover cyclometalation where a bidentate donor, such as 2,2'-bipyridine, upon C-H activation leads to a species with a free donor atom that is able to influence the properties, hence the reactivity, of the complex.
We explored the similarities/differences between classical and rollover cyclometalation to check the importance of the second nitrogen donor by comparing suitably substituted 2,2'-bipyridines and 2-phenylpyridines; moreover the properties of the ligands were tuned to investigate the impact of stereoelectronic modification on the C-H activation process.
The reactivity of the newly synthesized cyclometalates having formula [Pt(K2-NC)(CH3)(L)] (κ2-N,C = cyclometalated ligand, L = neutral ligand) was tested in different conditions: ligand substitutions, protonolysis, oxidative additions and reductive eliminations. A wide variety of mono and dinuclear complexes was obtained and fully characterized by NMR spectroscopy.
Further insight has been sought from in silico experiments using DFT calculations that led to a nice agreement with the chemistry observed.
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