Yadav, Ravi and Janssen, Paul and Schorpp, Marcel and Greb, Lutz (2023) Calix[4]pyrrolato-germane-(thf)2: Unlocking the Anti-van’t Hoff–Le Bel Reactivity of Germanium(IV) by Ligand Dissociation. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 145 (32). pp. 17746-17754. ISSN 0002-7863, 1520-5126
Full text not available from this repository. (Request a copy)Abstract
Anti-van't Hoff-Le Bel configured p-blockelementspecies possess intrinsically high reactivity and are thus challengingto isolate. Consequently, numerous elements in this configuration,including square-planar germanium(IV), remain unexplored. Herein,we follow a concept to reach anti-van't Hoff-Le Belreactivity by ligand dissociation from a rigid calix[4]pyrrole germanein its bis(thf) adduct. While the macrocyclic ligand assures square-planarcoordination in the uncomplexed form, the labile thf donors providerobustness for isolation on a multigram scale. Unique properties ofa low-lying acceptor orbital imparted to germanium(IV) can be verified,e.g., by isolating an elusive anionic hydrido germanate and exploitingit for challenging bond activations. Aldehydes, water, alcohol, anda CN triple bond are activated for the first time by germanium-ligandcooperativity. Unexpected behaviors against fluoride ion donors disclosecritical interferences of a putative redox-coupled fluoride ion transferduring the experimental determination of Lewis acidity. Overall, weshowcase how ligand lability grants access to the uncharted chemistryof anti-van't Hoff-Le Bel germanium(IV) and line upthis element as a member in the emerging class of structurally constrainedp-block elements.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | BOND ACTIVATION; REDOX CHEMISTRY; C-H; PORPHYRINOGEN; COMPLEXES; OXIDATION; HYDRIDES; AMMONIA; FORMS; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 12 Mar 2024 11:58 |
| Last Modified: | 12 Mar 2024 11:58 |
| URI: | https://pred.uni-regensburg.de/id/eprint/59832 |
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