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Trabitsch, Karolina ; Ziegler, Christoph G. P. ; Prock, Lukas ; Balázs, Gábor ; Schwedtmann, Kai ; García-Padilla, Eduardo ; Meurer, Florian ; Snabilié, Demi D. ; de Bruin, Bas ; Weigand, Jan J. ; Wolf, Robert

Inorganic Cobalt Sandwich Complex [(η5-P5)Co(η3-P3)]−

Artikel

Trabitsch, Karolina, Ziegler, Christoph G. P., Prock, Lukas, Balázs, Gábor , Schwedtmann, Kai, García-Padilla, Eduardo, Meurer, Florian , Snabilié, Demi D., de Bruin, Bas , Weigand, Jan J. und Wolf, Robert (2026) Inorganic Cobalt Sandwich Complex [(η5-P5)Co(η3-P3)]−. Journal of the American Chemical Society 148 (11), S. 11467-11472.

DOI zum Zitieren dieses Dokuments: 10.5283/epub.79441


Zusammenfassung

Sandwich compounds are foundational to organometallic chemistry, yet carbon-free analogs remain exceptionally rare. We report the all-phosphorus heteroleptic cobalt sandwich anion [(η5-P5)Co(η3-P3)]− (4), obtained via a stepwise P4 activation/unmasking sequence in which (nacnac′)SiP4 serves as a controllable, silicon-protected P4 synthon. Reaction with the cobalt(−I) complex ...

Sandwich compounds are foundational to organometallic chemistry, yet carbon-free analogs remain exceptionally rare. We report the all-phosphorus heteroleptic cobalt sandwich anion [(η5-P5)Co(η3-P3)]− (4), obtained via a stepwise P4 activation/unmasking sequence in which (nacnac′)SiP4 serves as a controllable, silicon-protected P4 synthon. Reaction with the cobalt(−I) complex [K(THF)0.2][Co(η2:η2-cod)2] furnishes a bis(silatetraphosphacyclopentadienyl) cobaltate anion (1), and successive cleavage of the Si(nacnac′) units delivers the “naked” cyclo-P5/cyclo-P3 sandwich framework via monosilylated intermediates 2 and 3. The cryptate salts [M(crypt-222)]4 (M = Na, K) were characterized by 31P{1H} NMR spectroscopy, ESI-MS, and single-crystal X-ray diffraction (scXRD) for [Na(crypt-222)]4. In solution, 4 undergoes slow disproportionation to give the paramagnetic dianion [(η4-P5)Co(η3-P3)]2– (5), isolated as [K(crypt-222)]25 and authenticated by scXRD and EPR spectroscopy. Complexes 4 and 5 establish a deliberate strategy for accessing inorganic sandwich architectures and extend carbon-free metallocene chemistry to cobalt in two different oxidation states.



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Details

DokumentenartArtikel
Titel eines Journals oder einer ZeitschriftJournal of the American Chemical Society
VerlagACS
Open Access ArtACS Hybrid
Band148
Nummer des Zeitschriftenheftes oder des Kapitels11
SeitenbereichS. 11467-11472
Datum13 März 2026
Veröffentlichungsdatum13 Mai 2026 16:22
InstitutionenChemie und Pharmazie > Institut für Anorganische Chemie
Chemie und Pharmazie > Institut für Anorganische Chemie > Arbeitskreis Prof. Dr. Robert Wolf
Identifikationsnummer
WertTyp
10.1021/jacs.6c00419DOI
Stichwörter / KeywordsAnions, Cobalt, Ligands, Nuclear magnetic resonance spectroscopy, Sandwich compounds
Dewey-Dezimal-Klassifikation500 Naturwissenschaften und Mathematik > 540 Chemie
StatusVeröffentlicht
BegutachtetJa, diese Version wurde begutachtet
An der Universität Regensburg entstandenJa
URN der UB Regensburgurn:nbn:de:bvb:355-epub-794413
Dokumenten-ID79441

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