Synthesis and Modular Reactivity of Low Valent Al/Zn Heterobimetallics Supported by Common Monodentate Amides.

Dankert, Fabian; Hevia, Eva (2024). Synthesis and Modular Reactivity of Low Valent Al/Zn Heterobimetallics Supported by Common Monodentate Amides. Chemistry: a European journal, 30(16), e202304336. Wiley 10.1002/chem.202304336

Text Chemistry_A_European_J_-_2024_-_Dankert_-_Synthesis_and_Modular_Reactivity_of_Low_Valent_Al_Zn_Heterobimetallics_Supported.pdf - Accepted Version Restricted to registered users only until 8 January 2025. Available under License Publisher holds Copyright. Download (4MB) | Request a copy

Recent advances on low valent main group metal chemistry have shown the excellent potential of heterobimetallic complexes derived from Al(I) to promote cooperative small molecule activation processes. A signature feature of these complexes is the use of bulky chelating ligands which act as spectators providing kinetic stabilization to their highly reactive Al-M bonds. Breaking new ground in this field, here we report the synthesis of novel unsupported Al/Zn bimetallics prepared by the selective formal insertion of AlCp* into the Zn-N bond of the utility zinc amides ZnR2 (R = HMDS, hexamethyldisilazide; or TMP, 2,2,6,6-tetramethylpiperidide). By systematically assessing the reactivity of the new [(R)(Cp*)AlZn(R)] bimetallics towards carbodiimides, structural and mechanistic insights have been gained on their ability to undergo insertion in their Zn-Al bond. Disclosing a dramatic ligand effect, when R = TMP, an isomerization process can be induced giving [(TMP)2AlZn(Cp*)] which displays a special reactivity towards carbodiimides and carbon dioxide involving both its Al-N bonds, leaving its Al-Zn bond untouched.

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