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Application of the Redox‐Transmetalation Procedure to Access Divalent Lanthanide and Alkaline‐Earth NHC Complexes**

Schwarz, Noah 1; Sun, Xiaofei 1; Yadav, Ravi 1; Köppe, Ralf 1; Simler, Thomas 1; Roesky, Peter W. 1
1 Institut für Anorganische Chemie (AOC), Karlsruher Institut für Technologie (KIT)


Divalent lanthanide and alkaline-earth complexes supported by N-heterocyclic carbene (NHC) ligands have been accessed by redox-transmetalation between air-stable NHC-AgI complexes and the corresponding metals. By using the small ligand 1,3-dimethylimidazol-2-ylidene (IMe), two series of isostructural complexes were obtained: the tetra-NHC complexes [LnI2(IMe)4] (Ln=Eu and Sm) and the bis-NHC complexes [MI$_{2}$(IMe)$_{2}$(THF)$_{2}$] (M=Yb, Ca and Sr). In the former, distortions in the NHC coordination were found to originate from intermolecular repulsions in the solid state. Application of the redox-transmetalation strategy with the bulkier 1,3-dimesitylimidazol-2-ylidene (IMes) ligand yielded [SrI$_{2}$(IMes)(THF)$_{3}$], while using a similar procedure with Ca metal led to [CaI$_{2}$(THF)$_{4}$] and uncoordinated IMes. DFT calculations were performed to rationalise the selective formation of the bis-NHC adduct in [SrI$_{2}$(IMe)$_{2}$(THF)$_{2}$] and the tetra-NHC adduct in [SmI$_{2}$(IMe)$_{4}$]. Since the results in the gas phase point towards preferential formation of the tetra-NHC complexes for both metal centres, the differences between both arrangements are a result of solid-state effects such as slightly different packing forces.

Verlagsausgabe §
DOI: 10.5445/IR/1000137274
Veröffentlicht am 08.09.2021
DOI: 10.1002/chem.202101923
Zitationen: 8
Web of Science
Zitationen: 8
Zitationen: 8
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Anorganische Chemie (AOC)
Publikationstyp Zeitschriftenaufsatz
Publikationsdatum 06.09.2021
Sprache Englisch
Identifikator ISSN: 0947-6539, 1521-3765
KITopen-ID: 1000137274
Erschienen in Chemistry - a European journal
Verlag John Wiley and Sons
Band 27
Heft 50
Seiten 12857–12865
Vorab online veröffentlicht am 24.06.2021
Nachgewiesen in Scopus
Web of Science
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