Cobalt(II) and Manganese(II) Nitrosyl Complexes as Potential HNO/NOˉ Donor
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2024
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Abstract
This dissertation addresses our attempt to understand the potential of Co(II) and Mn(II) nitrosyl complexes as nitroxyl (HNO/NOˉ) donors. A series of nitrosyl complexes were synthesized by varying the ligand framework (from electron deficient to electron rich) with a central metal ion (e.g. Co2+ and Mn2+). The ability of these metal-nitrosyl complexes to act as HNO/NOˉ donors under different reaction conditions was discussed in chapters 2 to 5. The potential of cobalt-nitrosyl complexes as nitroxyl donors was extensively discussed in chapters 2 to 4, whereas chapter 5 addresses the manganese-nitrosyl complex, which led to some significant observations. For instance, in chapter 2, the nitroxyl releasing ability of a {Co(NO)}8 complex in presence of anionic sixth ligands like BF4ˉ and DTCˉ was observed, which is the first example of such kind of reaction. Chapter 3 describes our in detailed findings of the reaction between a {Co(NO)}8 complex and DTCˉ anion, which also leads to the NOˉ donation. In chapter 4, a neutral imidazole ligand mediated NOˉ release from a highly electron rich {Co(NO)}8
complex was studied. All of these sixth ligand mediated nitroxyl release from cobalt-nitrosyl complexes
are found to be concomitant in nature. The kinetic inertness of low-spin d6 cobalt-centre of {Co(NO)}8 complexes makes the release of HNO very difficult. Our recent findings on the methodology for HNO/NOˉ release from {Co(NO)}8 complexes will contribute significantly to the existing knowledge of nitroxyl donation from cobalt-nitrosyl complexes.
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Supervisor: Mondal, Biplab