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Synthesis, electronic structure and reactivity of rhodium(I) and iridium(I) bis(imino)acenaphthene complexes
Thesis (PhD (Chemistry))--University of Pretoria, 2022.
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University of Pretoria
2023
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| _version_ | 1867613622728916992 |
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| access_status_str | Open Access |
| author2 | Bezuidenhout, Daniela I. |
| author_browse | Bezuidenhout, Daniela I. |
| author_facet | Bezuidenhout, Daniela I. |
| collection | Thesis |
| dc_rights_str_mv | © 2023 University of Pretoria. All rights reserved. The copyright in this work vests in the University of Pretoria. No part of this work may be reproduced or transmitted in any form or by any means, without the prior written permission of the University of Pretoria. |
| description | Thesis (PhD (Chemistry))--University of Pretoria, 2022. |
| format | Thesis |
| id | oai:repository.up.ac.za:2263/91407 |
| institution | University of Pretoria (South Africa) |
| language | English |
| last_indexed | 2026-06-10T12:39:04.809Z |
| license_str | Other — see source repository |
| provenance_str_mv | Harvested via OAI-PMH from UPSpace — University of Pretoria Institutional Repository |
| publishDate | 2023 |
| publishDateRange | 2023 |
| publishDateSort | 2023 |
| publisher | University of Pretoria |
| publisherStr | University of Pretoria |
| record_format | dspace |
| source_str | UPSpace — University of Pretoria Institutional Repository |
| spelling | oai:repository.up.ac.za:2263/91407 Synthesis, electronic structure and reactivity of rhodium(I) and iridium(I) bis(imino)acenaphthene complexes Bezuidenhout, Daniela I. louw.wynandjohannes@gmail.com Radhakrishnan, Shankara G. Louw, Wynand Johannes UCTD Rhodium(I) Iridium(I) BIAN complexes Redox non-innocent CO2 reduction Thesis (PhD (Chemistry))--University of Pretoria, 2022. The bis(arylimino)acenaphthalene (BIAN) group of α-diimine compounds has shown promising electron sink behaviour and redox non-innocent activity as ligands to main group and transition metals. Here we present a series of rhodium(I) and iridium(I) complexes of BIAN derivatives with 2,6-diisopropylphenyl (DippBIAN, DB) and 2,4,6-trimethylphenyl (MesBIAN, MB), featuring various electron withdrawing and donating ancillary ligands. The crystal structures of square planar complexes 1b [RhMB(cod)]PF6, 1d [IrMB(cod)]PF6, 2a [RhDB(CO)2]PF6, 2b [RhMB(CO)2]PF6, 2c [IrDB(CO)2]PF6 and 3a [RhDB(CO)(PEt3)]PF6 are reported, as well as the square pyramidal structure of 4c [IrDB(cod)Cl]. The C–N and C–C bond lengths within the bisimine moiety for the structures of 2a and 4c suggest that the DippBIAN ligands are present in a reduced state, however, all other data from our multi-technique analyses correspond to results for neutral BIAN ligands. These contrasting results are indicative of the DippBIAN’s non-innocent behaviour, accepting additional electron density from the metal centre due to push-pull mechanism between the ancillary and BIAN ligands. The electrochemical study in non-coordinating solvent CH2Cl2 revealed that all complexes featured at least one reversible, ligand-centred reduction event at less negative potentials (above –1.0 V vs Ag/Ag+). In addition, preliminary results from our electrocatalytic CO2 reduction study has shown a promising interaction between CO2 and complex 3a, paving the way for exploring heterogeneous catalysis on these class of compounds. In addition, the statistically-based Peak Characterisation Model (PCM) was developed from Linear Free Energy Relationships (LFERs) between experimentally recorded DPV peak potentials, and various calculated theoretical properties of each reported compound. The PCM aided differentiation between voltammetric peaks associated with the primary electrochemical reaction of the analyte and voltammetry peaks of impurities or secondary reactions in the electrolyte solution. University of Pretoria Postgraduate Bursaries Sasol Technology R&D Pty. Ltd. South African National Research Foundation (NRF), via the CSUR funding element, UID: 116317 South African National Research Foundation (NRF), via the Renewable and Sustainable Energy Masters and Doctoral Scholarship Chemistry PhD (Chemistry) Unrestricted 2023-07-13T10:09:41Z 2023-07-13T10:09:41Z 2023-09-01 2022 Thesis * S2023 http://hdl.handle.net/2263/91407 DOI: https://doi.org/10.25403/UPresearchdata.23668158.v1 10.25403/UPresearchdata.23668158 en © 2023 University of Pretoria. All rights reserved. The copyright in this work vests in the University of Pretoria. No part of this work may be reproduced or transmitted in any form or by any means, without the prior written permission of the University of Pretoria. application/pdf University of Pretoria |
| spellingShingle | UCTD Rhodium(I) Iridium(I) BIAN complexes Redox non-innocent CO2 reduction Synthesis, electronic structure and reactivity of rhodium(I) and iridium(I) bis(imino)acenaphthene complexes |
| title | Synthesis, electronic structure and reactivity of rhodium(I) and iridium(I) bis(imino)acenaphthene complexes |
| title_full | Synthesis, electronic structure and reactivity of rhodium(I) and iridium(I) bis(imino)acenaphthene complexes |
| title_fullStr | Synthesis, electronic structure and reactivity of rhodium(I) and iridium(I) bis(imino)acenaphthene complexes |
| title_full_unstemmed | Synthesis, electronic structure and reactivity of rhodium(I) and iridium(I) bis(imino)acenaphthene complexes |
| title_short | Synthesis, electronic structure and reactivity of rhodium(I) and iridium(I) bis(imino)acenaphthene complexes |
| title_sort | synthesis electronic structure and reactivity of rhodium i and iridium i bis imino acenaphthene complexes |
| topic | UCTD Rhodium(I) Iridium(I) BIAN complexes Redox non-innocent CO2 reduction |
| url | http://hdl.handle.net/2263/91407 |