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Inorganic Cobalt Sandwich Complex [(η5-P5)Co(η3-P3)]−
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.
Veröffentlichungsdatum dieses Volltextes: 13 Mai 2026 16:22
Artikel
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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| Dokumentenart | Artikel | ||||
| Titel eines Journals oder einer Zeitschrift | Journal of the American Chemical Society | ||||
| Verlag: | ACS | ||||
|---|---|---|---|---|---|
| Band: | 148 | ||||
| Nummer des Zeitschriftenheftes oder des Kapitels: | 11 | ||||
| Seitenbereich: | S. 11467-11472 | ||||
| Datum | 13 März 2026 | ||||
| Institutionen | Chemie und Pharmazie > Institut für Anorganische Chemie Chemie und Pharmazie > Institut für Anorganische Chemie > Arbeitskreis Prof. Dr. Robert Wolf | ||||
| Identifikationsnummer |
| ||||
| Stichwörter / Keywords | Anions, Cobalt, Ligands, Nuclear magnetic resonance spectroscopy, Sandwich compounds | ||||
| Dewey-Dezimal-Klassifikation | 500 Naturwissenschaften und Mathematik > 540 Chemie | ||||
| Status | Veröffentlicht | ||||
| Begutachtet | Ja, diese Version wurde begutachtet | ||||
| An der Universität Regensburg entstanden | Ja | ||||
| URN der UB Regensburg | urn:nbn:de:bvb:355-epub-794413 | ||||
| Dokumenten-ID | 79441 |
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