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]
- Standort
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Deutsche Nationalbibliothek Frankfurt am Main
- Umfang
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Online-Ressource
- Sprache
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Englisch
- Anmerkungen
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Chemical science. - 13, 41 (2022) , 12078-12086, ISSN: 2041-6539
- Ereignis
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Veröffentlichung
- (wo)
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Freiburg
- (wer)
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Universität
- (wann)
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2022
- Urheber
- Beteiligte Personen und Organisationen
- DOI
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10.1039/d2sc04637g
- URN
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urn:nbn:de:bsz:25-freidok-2307493
- Rechteinformation
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Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
- Letzte Aktualisierung
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25.03.2025, 13:49 MEZ
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Entstanden
- 2022
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