Divergent Chemistry of Ditetrelynes (E2R2, E = Si, Ge) with Late Transition Metals and Low-valent Silicon Precursors
Divergent Chemistry of Ditetrelynes (E2R2, E = Si, Ge) with Late Transition Metals and Low-valent Silicon Precursors
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dc.contributor.advisor | Filippou, Alexander C. | |
dc.contributor.author | Palui, Prasenjit | |
dc.date.accessioned | 2024-06-12T09:19:42Z | |
dc.date.available | 2024-06-12T09:19:42Z | |
dc.date.issued | 12.06.2024 | |
dc.identifier.uri | https://hdl.handle.net/20.500.11811/11596 | |
dc.description.abstract | In modern inorganic chemistry, achieving “gram-scale syntheses” of compounds featuring elements in unusually low oxidation states with unconventional bonding modes continues to be a central goal. Successful isolation of such compounds requires novel synthetic approaches and well-designed sterically demanding substituents to provide kinetic protection. The heavy analogues of alkynes, the “ditetrelynes” stand out as notable examples in this category. They exhibit a trans-bent core with a small HOMO–LUMO gap (∼2 eV) and partial diradical character. This unusual bonding of ditetrelynes renders them intriguing in terms of reactivity, and they have proven effective in small molecule activation, C-C coupling reactions, and even in catalysis. Within this framework, efforts will concentrate on pioneering new synthetic methodologies for the formation of heavier tetrel-element multiple bonds via activation/cleavage of ditetrelynes (E2R2, E = Si, Ge). In this work the high synthetic potential of Ge2Tbb2 and Si2Tbb2 was tested towards metal-carbonyls to synthesize and characterize novel unsaturated metallacycles (1-Co, 1-Rh, 5-Co, 9-Rh, 10-Co, 16-Co, 21-Rh) containing low-valent Si and Ge, and exploring their further reactivity, giving the first examples of inverted-carbene complexes (26-Co and 26-Rh) and a disilacyclopropenone complex (27-Rh). Moving further with the ditetrelyne chemistry, unprecedented bis-tetrylidene (31-Ni), tetrylidene-tetrylidyne (29-Co, 32-Ni), and bis-tetrylidyne (30-Co, 33-Fe, 34-Fe) complexes were synthesized and characterized via “Ge≡Ge” triple bond cleavage of a digermyne at a single metal center (M = Fe, Co, Ni). Finally, using a transition metal free metathesis reaction of a “Ge≡Ge” triple bond, a caacMe-supported germasilyne (35-Si) was synthesized and exploring its unique reactivity led to the isolation of novel compounds such as a cationic silagermavinylidene (39-Si) and a potassium silenide (40-Si). The chemistry of silagermavinylidene helped further to isolate the germasilyne (43-Si), which showed a unique isomerization reaction to its vinylidenic form (44-Si) via caacMe and halide migration. This transformation can be considered as an inverse reminiscent of the FBW-rearrangement in context of heavier tetrel chemistry. | en |
dc.language.iso | eng | |
dc.rights | In Copyright | |
dc.rights.uri | http://rightsstatements.org/vocab/InC/1.0/ | |
dc.subject | low-valent | |
dc.subject | heavier main group | |
dc.subject | unsaturated-metallacycle | |
dc.subject | silylidyne | |
dc.subject | bis-silylidene | |
dc.subject | bis-germylidyne | |
dc.subject | late transition metal | |
dc.subject | germasilyne | |
dc.subject | silenide | |
dc.subject | disilenide | |
dc.subject | isocyanide coupling | |
dc.subject | disilacyclopropenone | |
dc.subject | digermyne | |
dc.subject | disilyne | |
dc.subject | vinylidene | |
dc.subject | inverted carbene | |
dc.subject | CAAC | |
dc.subject | NHC | |
dc.subject | metathesis | |
dc.subject.ddc | 540 Chemie | |
dc.title | Divergent Chemistry of Ditetrelynes (E2R2, E = Si, Ge) with Late Transition Metals and Low-valent Silicon Precursors | |
dc.type | Dissertation oder Habilitation | |
dc.identifier.doi | https://doi.org/10.48565/bonndoc-300 | |
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:5-76547 | |
ulbbn.pubtype | Erstveröffentlichung | |
ulbbnediss.affiliation.name | Rheinische Friedrich-Wilhelms-Universität Bonn | |
ulbbnediss.affiliation.location | Bonn | |
ulbbnediss.thesis.level | Dissertation | |
ulbbnediss.dissID | 7654 | |
ulbbnediss.date.accepted | 05.06.2024 | |
ulbbnediss.institute | Mathematisch-Naturwissenschaftliche Fakultät : Fachgruppe Chemie / Institut für Anorganische Chemie | |
ulbbnediss.fakultaet | Mathematisch-Naturwissenschaftliche Fakultät | |
dc.contributor.coReferee | Bismuto, Alessandro | |
ulbbnediss.contributor.orcid | https://orcid.org/0000-0001-9755-8446 |
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