Synthesis, reactions and redox properties of 1,4-dihydro-1,4-diphosphinines and related P/Si- and P/Ge-compounds
Synthesis, reactions and redox properties of 1,4-dihydro-1,4-diphosphinines and related P/Si- and P/Ge-compounds
dc.contributor.advisor | Streubel, Rainer | |
dc.contributor.author | Kottayil Madam Ramachandran, Mridhul Ram | |
dc.date.accessioned | 2023-11-16T16:32:57Z | |
dc.date.available | 2023-11-16T16:32:57Z | |
dc.date.issued | 16.11.2023 | |
dc.identifier.uri | https://hdl.handle.net/20.500.11811/11138 | |
dc.description.abstract | 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. | en |
dc.language.iso | eng | |
dc.rights | In Copyright | |
dc.rights.uri | http://rightsstatements.org/vocab/InC/1.0/ | |
dc.subject | 1,4-Diphosphinine | |
dc.subject | 1,4-Dihydro-1,4-phosphasiline | |
dc.subject | 1,4-Dihydro-1,4-phosphagermine | |
dc.subject | 1,4-Phosphasiline | |
dc.subject | DFT | |
dc.subject | Aromaticity | |
dc.subject | Cyclic Voltammetry | |
dc.subject.ddc | 540 Chemie | |
dc.title | Synthesis, reactions and redox properties of 1,4-dihydro-1,4-diphosphinines and related P/Si- and P/Ge-compounds | |
dc.type | Dissertation oder Habilitation | |
dc.identifier.doi | https://doi.org/10.48565/bonndoc-160 | |
dc.publisher.name | Universitäts- und Landesbibliothek Bonn | |
dc.publisher.location | Bonn | |
dc.rights.accessRights | openAccess | |
dc.identifier.urn | https://nbn-resolving.org/urn:nbn:de:hbz:5-72898 | |
dc.relation.doi | https://doi.org/10.1039/D3DT00850A | |
dc.relation.doi | https://doi.org/10.1021/acs.inorgchem.1c03620 | |
dc.relation.doi | https://doi.org/10.1002/ejic.202300573 | |
ulbbn.pubtype | Erstveröffentlichung | |
ulbbnediss.affiliation.name | Rheinische Friedrich-Wilhelms-Universität Bonn | |
ulbbnediss.affiliation.location | Bonn | |
ulbbnediss.thesis.level | Dissertation | |
ulbbnediss.dissID | 7289 | |
ulbbnediss.date.accepted | 17.10.2023 | |
ulbbnediss.institute | Mathematisch-Naturwissenschaftliche Fakultät : Fachgruppe Chemie / Institut für Anorganische Chemie | |
ulbbnediss.fakultaet | Mathematisch-Naturwissenschaftliche Fakultät | |
dc.contributor.coReferee | Schiemann, Olav | |
ulbbnediss.contributor.orcid | https://orcid.org/0000-0002-7869-4861 |
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