Phosphorus/Antimony and Phosphorus/H-bond Donor Ambiphilic Ligands: Incorporation into Late Transition Metal Complexes and the Reactivity Thereof
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Z-type ligands based on main group Lewis acids like Sb(V), B(III) and Al(III) etc. have heralded a new direction in the coordination chemistry of transition metals. Although ambiphilic ligands featuring group 13 and 14 main group elements have been explored in the realm of coordination chemistry of late transition metals, utilization of heavy group 15 elements remains mostly limited to L-type spectator ligands. Recent research on transition metal/antimony platforms has shown that the electronic properties of the transition metal centers can be successfully modulated with the help of carefully crafted Lewis acidic ligands due to their versatile redox and coordination non-innocent properties. In this dissertation, I have studied the structure-property correlation in a series of heterobimetallic platforms featuring antimony-based Z-ligands with tunable stereo-electronic properties. This dissertation delineates the investigation of the effects of strongly Lewis acidic antimony center on the coordination chemistry and the reactivity of the ligated metal center in a series of [Sb-M] compounds. A systematic analysis of the Lewis acidity, coordination properties and the catalytic activities of the Sb-M complexes proved that the variation of the substituents at antimony and phosphorus plays a significant role in the bonding and electron distribution between the Lewis acid and the transition metal center and this modulation of electronic properties has been exploited for electrophilic catalysis as well as for the photoreductive elimination of halogens. My second project is inspired by the basic concept that the metal-ligand cooperativity plays an important role in enhancing the catalytic activities of the metal centers. Recent development in gold catalysis focusses on new methods to bypass the use of silver salt metathesis by introducing metal-ligand cooperativity in gold complexes. I have discovered a novel route to self-activate the gold center and overcome the synthetic difficulties posed by the use of light- and moisture-sensitive silver salts in gold catalysis by introducing a H-bond donor functional group in the ligand framework to provide.
Sen, Srobona (2017). Phosphorus/Antimony and Phosphorus/H-bond Donor Ambiphilic Ligands: Incorporation into Late Transition Metal Complexes and the Reactivity Thereof. Doctoral dissertation, Texas A & M University. Available electronically from