Kottayil Madam Ramachandran, Mridhul Ram: Synthesis, reactions and redox properties of 1,4-dihydro-1,4-diphosphinines and related P/Si- and P/Ge-compounds. - Bonn, 2023. - Dissertation, Rheinische Friedrich-Wilhelms-Universität Bonn.
Online-Ausgabe in bonndoc: https://nbn-resolving.org/urn:nbn:de:hbz:5-72898
urn: https://nbn-resolving.org/urn:nbn:de:hbz:5-72898,
doi: https://doi.org/10.48565/bonndoc-160,
author = {{Mridhul Ram Kottayil Madam Ramachandran}},
title = {Synthesis, reactions and redox properties of 1,4-dihydro-1,4-diphosphinines and related P/Si- and P/Ge-compounds},
school = {Rheinische Friedrich-Wilhelms-Universität Bonn},
year = 2023,
month = nov,

note = {This Ph.D. thesis describes the P-centered as well as other heteroatom-centered reactions of mixed-atom heterocyclic compounds.
Initially, the synthesis of the anionic imidazole-2-thione-fused 1,4-dihydro-1,4-diphosphinines from 1,4-diphosphinine and the methylation reactions targeting the anionic P-centers to form the methylated products were explored. In addition, their P-centered redox process was investigated in detail via Cyclic Voltammetry experiments and theoretical calculations. Secondly, novel tricyclic 1,4-dihydro-1,4-phosphasiline and -1,4-phosphagermine derivatives were synthetically targeted by the backbone lithiation of 4-bis(diorganoamino)silanyl-and 4- bis(diorgano-amino)germanyl-substituted imidazole-2-thiones. P-centered redox processes of 1,4-dihydro-1,4-phosphasiline derivatives were investigated via Cyclic Voltammetry experiments and theoretical calculations. The conversion of the anionic imidazole-2-thione-fused 1,4-dihydro-1,4-phosphasilines into its Si(NR2)2 derivative by the addition of triphenylmethyl chloride and, subsequently, into its SiCl2-containing derivative by the addition of an HCl ether solution was also investigated. The latter was further derivatized on the Si-center by the addition of methyllithium and methanol. The SiCl2-containing derivative was further subjected to reduction reactions involving the Si-center and the trapping reactions of the transient silylene species with 1,3- butadiene were also investigated. Finally, the synthesis of the 1,4,4’-trichloro substituted 1,4-dihydro-1,4-phosphasiline was discussed. It was subjected to reduction reactions to synthesize the first example of an aromatic 1,4-phosphasiline derivative which led to limited success as the final product could not be isolated.},

url = {https://hdl.handle.net/20.500.11811/11138}

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