Reactions of [ZnR₂(L)] Complexes with Dioxygen: A New Look at an Old Problem

Abstract

OR or OOR? The oxygenation of ZntBu2 in the presence of donor ligands demonstrates the tendency of zinc dialkyls to undergo oxidation of only one ZnC bond under controlled conditions (see scheme). The formation of alkoxide or peroxide species is influenced by the type of donor ligand employed, and these divergent pathways offer a glimpse into the general mechanism of dioxygen activation.

A New Method for the Growth of Zinc Oxide Nanowires by MOCVD using Oxygen‐Donor Adducts of Dimethylzinc

“…[21] The relative base strength of [NEt 3 ] is approximately three times higher than THF, [22] which in turn is a stronger base than THP or furan. [20] [24] and, significantly, four-coordinate alkylzinc complexes of this type have been shown to be resistant to further oxidation. [24] Fig.…”

“…[20] [24] and, significantly, four-coordinate alkylzinc complexes of this type have been shown to be resistant to further oxidation. [24] Fig. 2).…”

Facile Low‐Temperature Approach to Tin‐Containing ZnO Nanocrystals with Tunable Tin Concentrations Using Heterobimetallic Sn/Zn Single‐Source Precursors

“…The synthesis and characterization of sterically demanding triphenyltin‐alkylzinc‐alkoxy compounds [Ph 3 SnOZnR] 4 (R=Me ( 1 ), Et ( 2 )) are presented. Furthermore, the steric congestion at the zinc atoms in [R 3 SnOZn t Bu] 4 was increased in compound 3 and 4 .Therefore, triorganotin hydroxides R 3 SnOH (R=Me, Ph) were treated with appropriate alkylzinc Lewis bases ZnR’ 2 (R’=Me, Et, t Bu) 14. Products 1 and 2 were isolated as colorless crystals in good yields (70–82 %; Scheme ).…”

Dimethylzinc adduct chemistry revisited: MOCVD of vertically aligned ZnO nanowires using the dimethylzinc 1,4-dioxane adduct

“…It was shown that besides preventing pre-reaction with oxygen, the adducts also led to the deposition of vertically aligned ZnO nanowires on the Si(1 1 1) substrates at temperatures of $ 500 1C. It was proposed that pre-reaction is suppressed by the formation in the gas-phase of relatively oxygen-resistant species such as [MeZn(OMe)(L)] x , and this is supported by the recent isolation and structural characterization of the oxygen-resistant dimer [Bu t Zn(OBu t )(THF)] 2 [20]. The precise mechanism of ZnO nanowire growth from the [Me 2 Zn(L)] adducts has not been established, but it is proposed that alkylzinc alkoxide intermediates such as [MeZn(OMe)(L)] (L¼cyclic ether) and/or [MeZn(OMe)] play a key role in the gas-phase and surface kinetics of ZnO nanowire formation [19].…”