Donor Functionalized N-Heterocyclic Carbene and Olefin Complexes in the Lights of Bismuth

Guha Roy, Anisha (2025) Donor Functionalized N-Heterocyclic Carbene and Olefin Complexes in the Lights of Bismuth. Masters thesis, Indian Institute of Science Education and Research Kolkata.

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Abstract

This thesis deals with the synthesis of donor functionalized N-Heterocyclic Carbene (NHC) and N-Heterocyclic Olefin (NHO) bismuth complexes along with their spectroscopic studies. N-heterocyclic olefins (NHOs) are emerging as strong competitors to N-heterocyclic carbenes (NHCs), but their development lags in donor-functionalization, a key factor for expanding their applications. Few examples exist, mostly with donors at the N-wingtips, but mostly suffer from stability issues. N-heterocyclic olefins (NHOs), derived from NHCs, exhibit unique properties such as high nucleophilicity and basicity. After a period of dormancy, NHOs have gained significant interest over the past years, showing their potential in various applications, including catalysis, CO2 fixation, and polymerization, often surpassing NHCs. The second chapter of this thesis deals with the synthesis of NHC Bi and NHO Bi complexes by alternating the ratios of the reactants. By treating the previously reported bifunctional imidaozlium-phenol, LH2Br, and Bi(HMDS)3 in a 1:1 ratio, the NHC-Bi complex is obtained. While, reacting LH2Br, Bi(HMDS)3, and KHMDS in a 2:1:1 relative ratio forms a new NHO-Bi complex. The tridentate dianionic and N-Heterocyclic Olefin ligand class is highly remarkable for its unsymmetric nature and uniqueness. Further, the same NHO framework is synthesized via a more independent and general route by varying the substitution to prove the concept.

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