From mixed group 13 cations [M(AlCp*)3]+ (M = Ga/In/Tl) to an Al4+ cluster
Abstract: AlCp*-complexes with transition metals have shown to be highly reactive and enable C–H or Si–H bond activation. Yet, complexes of AlCp* with low-valent main-group metals are scarce. Here, we report the syntheses of [M(AlCp*)3][Al(ORF)4] (RF = C(CF3)3) with M = Ga, In, Tl, which include the first covalent Al–In and Al–Tl bonds. For M = Ga, AlCp*-coordination induced the formation of the dication [Ga2(AlCp*)6]2+ in the solid state, which exhibits a solvent and temperature dependent monomer–dimer equilibrium in solution. By contrast, the In and Tl complexes are monomeric and prone to reduction to the metal by the electron-rich AlCp*-moieties. The QTAIM analysis suggests that the metal centres are already highly reduced in the complexes, while the positive charge is distributed onto the AlCp* units. Addition of Me3TACN (1,4,7-trimethyl-1,4,7-triazacyclononane) to the Ga- and Tl-complex salts resulted in an isomerization to the novel low-valent Al4+ cation [(Me3TACN)Al(AlCp*)3][Al(ORF)4]. Intermittently formed tetrahedral GaAl3+ clusters could be structurally characterized. From a detailed mechanistic study of this isomerization, the very high yield and clean preparation of [(Me3TACN)Al(AlCp*)3][Al(ORF)4] was devised from [M(Me3TACN)][Al(ORF)4] (M = Ga, Tl) and [(AlCp*)4]
- Location
-
Deutsche Nationalbibliothek Frankfurt am Main
- Extent
-
Online-Ressource
- Language
-
Englisch
- Notes
-
Chemical science. - 13, 41 (2022) , 12078-12086, ISSN: 2041-6539
- Event
-
Veröffentlichung
- (where)
-
Freiburg
- (who)
-
Universität
- (when)
-
2022
- Creator
- DOI
-
10.1039/d2sc04637g
- URN
-
urn:nbn:de:bsz:25-freidok-2307493
- Rights
-
Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
- Last update
-
25.03.2025, 1:49 PM CET
Data provider
Deutsche Nationalbibliothek. If you have any questions about the object, please contact the data provider.
Associated
Time of origin
- 2022
Other Objects (12)
Beiträge zur Chemie des Aluminiums : Synthese, Struktur und Reaktivität monomerer Aminoalane, Additionsverbindungen der Aluminiumhalogenide
Chemie mit schwach koordinierenden Anionen : Synthese einer neuen Klasse schwach koordinierender Anionen des Typs Al(ORF)-4, Lewis-Säure-Base-Addukte der sehr schwachen Lewis-Basen S8, P4 und P4S3 mit dem Ag+-Kation von Ag[Al(ORF)4], von homopolyatomaren Phosphorkationen zu Al(ORF)-4-Salzen neuer binärer Phosphor-Halogen-Kationen mit Polyphosphorskelett
Stable salts of heteroleptic iron carbonyl/nitrosyl cations
Syntheses, characterization and application of a variety of ethylzinc-cations and zinc alkoxides
The synthesis of reactive gold(I) and phosphorus cations with nitrosyl salts of weakly coordinating anions
Silver-Selenium complexes and phosphorus cations stabilised by weakly coordinating anions : = Silber-Selen Komplexe und Phosphorkationen stabilisiert durch schwach koordinierende Anionen
From pentacarbonylcobalt(I) salts to piano-stool and sandwich cations
Synthesis of novel homoleptic and heteroleptic transition metal carbonyl and nitrosyl cations
Synthesis and structural characterization of Gallium(I) and Indium(I) cations coordinated by pentamethylethylenediamine
Homoatomic cations : From [P₅]⁺ to [P₉]⁺
Investigation of novel transition metal carbonyl cations and dinitrogen complexes
Synthesis of main-group cations: from Lewis acidic group 2 to low-valent group 13 compounds
Beiträge zur Chemie des Aluminiums : Synthese, Struktur und Reaktivität monomerer Aminoalane, Additionsverbindungen der Aluminiumhalogenide
Chemie mit schwach koordinierenden Anionen : Synthese einer neuen Klasse schwach koordinierender Anionen des Typs Al(ORF)-4, Lewis-Säure-Base-Addukte der sehr schwachen Lewis-Basen S8, P4 und P4S3 mit dem Ag+-Kation von Ag[Al(ORF)4], von homopolyatomaren Phosphorkationen zu Al(ORF)-4-Salzen neuer binärer Phosphor-Halogen-Kationen mit Polyphosphorskelett
Stable salts of heteroleptic iron carbonyl/nitrosyl cations
Syntheses, characterization and application of a variety of ethylzinc-cations and zinc alkoxides
The synthesis of reactive gold(I) and phosphorus cations with nitrosyl salts of weakly coordinating anions
Silver-Selenium complexes and phosphorus cations stabilised by weakly coordinating anions : = Silber-Selen Komplexe und Phosphorkationen stabilisiert durch schwach koordinierende Anionen
From pentacarbonylcobalt(I) salts to piano-stool and sandwich cations
Synthesis of novel homoleptic and heteroleptic transition metal carbonyl and nitrosyl cations
Synthesis and structural characterization of Gallium(I) and Indium(I) cations coordinated by pentamethylethylenediamine
Homoatomic cations : From [P₅]⁺ to [P₉]⁺
Investigation of novel transition metal carbonyl cations and dinitrogen complexes
Synthesis of main-group cations: from Lewis acidic group 2 to low-valent group 13 compounds
Beiträge zur Chemie des Aluminiums : Synthese, Struktur und Reaktivität monomerer Aminoalane, Additionsverbindungen der Aluminiumhalogenide
Chemie mit schwach koordinierenden Anionen : Synthese einer neuen Klasse schwach koordinierender Anionen des Typs Al(ORF)-4, Lewis-Säure-Base-Addukte der sehr schwachen Lewis-Basen S8, P4 und P4S3 mit dem Ag+-Kation von Ag[Al(ORF)4], von homopolyatomaren Phosphorkationen zu Al(ORF)-4-Salzen neuer binärer Phosphor-Halogen-Kationen mit Polyphosphorskelett
Stable salts of heteroleptic iron carbonyl/nitrosyl cations
Syntheses, characterization and application of a variety of ethylzinc-cations and zinc alkoxides
The synthesis of reactive gold(I) and phosphorus cations with nitrosyl salts of weakly coordinating anions
Silver-Selenium complexes and phosphorus cations stabilised by weakly coordinating anions : = Silber-Selen Komplexe und Phosphorkationen stabilisiert durch schwach koordinierende Anionen
From pentacarbonylcobalt(I) salts to piano-stool and sandwich cations
Synthesis of novel homoleptic and heteroleptic transition metal carbonyl and nitrosyl cations
Synthesis and structural characterization of Gallium(I) and Indium(I) cations coordinated by pentamethylethylenediamine
Homoatomic cations : From [P₅]⁺ to [P₉]⁺
Investigation of novel transition metal carbonyl cations and dinitrogen complexes