An In‐Depth Look at the Reactivity of Non‐Redox‐Metal Alkylperoxides

Abstract

Over the past 150 years,acertain mythology has arisen around the mechanistic pathwaysofthe oxygenation of organometallics with non-redox-active metal centers as well as the character of products formed. Notably,t here is aw idespread perception that the formation of commonly encountered metal alkoxide species results from the auto-oxidation reaction, in whichaparent metal alkylc ompound is oxidized by the metal alkylperoxide via oxygen transfer reaction. Now, harnessing awell-defined zinc ethylperoxide incorporating a bdiketiminate ligand, the investigated alkylperoxide compounds do not react with the parent metal alkyl complex as well as Et 2 Zn to form az inc alkoxide.U pon treatment of the zinc ethylperoxide with Et 2 Zn, ap reviously unobserved ligand exchange process is favored. Isolation of az inc hydroxide carboxylate as ap roduct of decomposition of the parent zinc ethylperoxide demonstrates the susceptibility of the latter to OÀ Ob ond homolysis.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Unveiling Complexity of the Oxygenation of Aluminum Alkyls by the Isolation of Unique Alkylperoxide and Oxoalkoxide Compounds

“…Very recently, we also shed new light on the above-mentioned autoxidation reaction of NR MOOR species and demonstrated that the well-defined ZnOOR compound reacts neither with a parent alkyl complex nor even with a homoleptic metal alkyl compound with formation of the respective metal alkoxides. 29 In fact, our investigations strongly indicate that formation of the metal alkoxides may be rationalized in terms of an intramolecular rearrangement of nonredox metal alkylperoxides ( Scheme 1 , path 2). 11 , 27 , 28 Moreover, considering the chemistry of NR MOOR species, particular mention should be made of the O–O bond scissions.…”

“… 11 , 27 , 28 Moreover, considering the chemistry of NR MOOR species, particular mention should be made of the O–O bond scissions. Although regularly overlooked, homolysis of the O–O bond appears to be the critical factor responsible for the formation of a vast array of products including metal oxide, 30 − 33 hydroxide, 27 , 34 , 35 and even carboxylate 29 , 32 clusters ( Scheme 1 , path 3).…”

A Case Study on the Desired Selectivity in Solid‐State Mechano‐ and Slow‐Chemistry, Melt, and Solution Methodologies

“…As a part of our ongoing interest in the radical chemistry of the non‐redox active metal‐based organometallic complexes [38–44] only very recently we demonstrated that TEMPO reacts smoothly with Et 2 Zn [45] (in solution) or t Bu 2 Zn [46] (in solution or solid state) compounds in solution by the single electron transfer (SET) step affording diamagnetic zinc complexes incorporating TEMPO anion (TEMPO*). Moreover, in the case of the solid‐state reactions involving the Ph 2 Zn/TEMPO system, mechano‐ and slow chemistry appeared as mutually complementary methods for the synthesis of the paramagnetic [Ph 2 Zn( η 1 ‐TEMPO)⋅TEMPO] and diamagnetic [PhZn( μ 2 ‐ η 1 : η 1 ‐TEMPO*)][PhZn( μ 2 ‐TEMPO*)] products (Figure 1a,b, respectively) [30] .…”

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

“…The OÀ O bond distances (1.466(5) Å, 1.485(5) Å) are consistent with that in 2 and fall in the typical range observed for the terminal zinc alkylperoxide systems. [22,25,26] Bearing in mind that alkylperoxide moiety usually acts as a bridging ligand in metal alkylperoxides incorporating aminoalcoholates, [16,18,27] the presence of the terminal alkylperoxide groups in 3 2 appears to be an unusual feature. The best of our knowledge, compound 3 2 is the first example of nonredox-metal alkylperoxide possessing the bridging aminoalcoholates ligand along with the terminal alkylperoxide groups.…”

“…[18] Remarkably, the simultaneous oxygenation and hydrolysis of organozinc aminoalcoholates paved the way for chiroptically active zinc oxide quantum dots. [19] Building on our continuous interest and expertise in both the organozincs chemistry [11,20,21] and dioxygen activation, [13,[22][23][24][25] herein, we confront two different methods of the synthesis of zinc alkoxides and alkylperoxides: the alcoholysis and oxygenation of alkylzinc aminoalcoholate. Harnessing the well-defined tert-butylzinc complex incorporating a bioactive pridinolum ligand, we demonstrate that while the alcoholysis approach does not result in the formation of discrete products, the controlled oxygenation of [(prinol)ZntBu] (1) (where prinol = deprotonted 1,1-diphenyl-3-(piperidin-1-yl)propan-1-ol) affords selectively two novel zinc alkylperoxides possessing unusual structural motifs in the solid state: a dinuclear adduct of a [(prinol)ZnOOtBu] specie with the parent [(prinol)ZntBu] complex and a novel dimer [(prinol)ZnOOtBu] 2 with terminal alkylperoxide groups.…”