Templat-gestützte Aktivierung kleiner Moleküle mit s-/p-Block bimetallischen Systemen
Zusammenfassung der Projektergebnisse
Aluminum is an exceptionally abundant metal in the earth’s crust. It may serve as a sustainable congener for catalysis and small molecule activation (SMA) processes due to several recent breakthroughs in molecular main-group chemistry. The investigation on low-valent aluminum (and in general group 13 elements) in relation to scission of strong bonds has rapidly evolved throughout the past few years. Throughout my studies enabled by this DFG funded project I contributed to the field and several new findings, thereof especially Al(I) transfer regimes at heterometal centres have been uncovered. The original idea of my proposal to accessing (cyclic) oligomers via multinuclear aluminylene (also alumylene) s-block complexes and small molecular building blocks did not meet with success, however, multinuclear species could indeed be obtained with hitherto unprecedented aluminyl (also alumanyl) type ligands based on common monodentate amides. The research was in the end mostly orientated towards late (“main group like”) transition metal centres. This was found being a promising approach in generating multinuclear systems including aluminum in its lower oxidation states and hence followed in detail. Based on [AlCp*]4, which was employed and proposed to be a suitable Al(I) source, a stepwise increase in nuclearity was achieved throughout the studies. First bimetallic, then trimetallic and eventually hexametallic new reactive species were generated at a heterometallic partner. The main congeners have been the metal aluminyls [(R)(Cp*)Al–Zn(R)] (R = HMDS, TMP; HMDS = hexamethyldisilazanide, TMP = 2,2,6,6-tetramethylpiperidide), [(Cp*)Zn–Al(TMP)2], [(Cp*)(HMDS)Al–Cu(PtBu3)], [(Cp*)(HMDS)Al]2Zn and [(Cp*)Al–Cu(Al(HMDS)2)]2 all of which have been examined towards their formation and reactivity towards small molecules based on experimental and theoretical means. The main conclusions that have been drawn are the following: (i) the insertion of aluminylene [AlCp*] at metal amides furnishes well-defined metal aluminyls that (ii) can have modular reactivity, (iii) may be formed reversibly and (iv) may act as an [AlCp*] transfer reagent. All project results have broad implications for reversibly formable aluminyl species and close a gap between molecular low-oxidation state aluminum and cluster chemistry. All findings set the basis for my independent research career as a group leader which is funded through the Liebig fellowship scheme. We currently are interested in designing Al(I) transfer for the generation of new reactive species with implications for SMA and catalysis.
Projektbezogene Publikationen (Auswahl)
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A Hexametallic Copper Aluminylene Aluminyl. American Chemical Society (ACS).
Dankert, Fabian; Kadriu, Arbias & Hevia, Eva
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Catch & Release of Al(I) at a Zinc Bis-Amide. American Chemical Society (ACS).
Dankert, Fabian; Sabater, Enric; Salvador, Pedro & Hevia, Eva
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Reductive‐Transmetalation Reactions of ZnR2/(AlCp*)4 Heterobimetallic Combinations and Application Towards CO2 Insertion. European Journal of Inorganic Chemistry, 27(31).
Hevia, Eva & Dankert, Fabian
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Synthesis and Modular Reactivity of Low Valent Al/Zn Heterobimetallics Supported by Common Monodentate Amides. Chemistry – A European Journal, 30(16).
Dankert, Fabian & Hevia, Eva
