Effectiveness of the Oxygenation over Classical Protonolysis Reactions: A Case of Alkylzinc Complexes Incorporating an Aminoalcoholate Ligand.

Zelga, Karolina; Pietrzak, Tomasz; Han, Tomasz; Justyniak, Iwona; Chwojnowska, Elżbieta; Sobota, Piotr; Lewiński, Janusz

Alkylzinc aminoalcoholates have emerged as powerful catalysts in organic synthesis and polymerization processes. Despite extensive research, difficulties in the rational design of these catalytic systems and in‐depth understanding of their modes of action have hitherto been encountered. Most of the major obstacles stem largely from the relatively limited knowledge of the structure‐activity relationship of zinc catalysts. In fact, the key active species are often generated in situ via the protonolysis of the alkylzinc precursors, which precludes their isolation and detailed characterization. Herein, the effectiveness of the oxygenation over the classical protonolysis in the synthesis of zinc alkylperoxides stabilized by an aminoalcoholate ligand is demonstrated. The controlled oxygenation of a tert‐butylzinc complex incorporating a pridinolum (prinol) ligand leads to well‐defined a dinuclear adduct of a (prinol)ZnOOtBu moiety with the parent tBuZn(prinol) complex and a novel dimer [tBuOOZn(prinol)]2 with terminal alkylperoxide groups. The observed reaction outcomes strongly depend on the reaction conditions. Although sparse examples of heteroleptic adducts of the [RZn(L)]x[ROOZn(L)]y‐type are known, the herein reported homoleptic [ROOZn(L)]x aggregate is unprecedented. Strikingly, comparative studies involving reactions between tBuZn(prinol) and tert‐butylhydroperoxide or ethanol revealed that the respective seemingly simple zinc alkylperoxides, or zinc alkoxides, respectively, are not accessible via the classical alcoholysis. We believe that these game‐changing results concerning multifaceted chemistry of organozinc aminoalcoholates should pave the way for more rational development of various Zn‐based catalytic systems.

OXYGEN in the blood; ZINC catalysts; CATALYST synthesis; ORGANIC synthesis; STRUCTURE-activity relationships; CATALYSTS; POLYMERIZATION

Chemistry - A European Journal, 2021, Vol 27, Issue 57, p14234

0947-6539

Academic Journal

10.1002/chem.202102172