1228657-47-3Relevant academic research and scientific papers
Remarkably robust monomeric alkylperoxyzinc compounds from tris(oxazolinyl)boratozinc alkyls and O2
Mukherjee, Debabrata,Ellern, Arkady,Sadow, Aaron D.
, p. 13018 - 13026 (2012/10/08)
Metal alkylperoxides are remarkable, highly effective, yet often thermally unstable, oxidants that may react through a number of possible pathways including O-O homolytic cleavage, M-O homolytic cleavage, nucleophilic O-atom transfer, and electrophilic O-atom transfer. Here we describe a series of zinc alkyl compounds of the type ToMZnR (ToM = tris(4,4-dimethyl-2-oxazolinyl)phenylborate; R = Et, n-C3H 7, i-C3H7, t-Bu) that react with O2 at 25 °C to form isolable monomeric alkylperoxides ToMZnOOR in quantitative yield. The series of zinc alkylperoxides is crystallographically characterized, and the structures show systematic variations in the Zn-O-O angle and O-O distances. The observed rate law for the reaction of ToMZnEt (2) and O2 is consistent with a radical chain mechanism, where the rate-limiting SH2 step involves the interaction of ?OOR and ToMZnR. In contrast, ToMZnH and ToMZnMe are unchanged even to 120 °C under 100 psi of O 2 and in the presence of active radical chains (e.g., ?OOEt). This class of zinc alkylperoxides is unusually thermally robust, in that the compounds are unchanged after heating at 120 °C in solution for several days. Yet, these compounds are reactive as oxidants with phosphines. Additionally, an unusual alkylperoxy group transfer to organosilanes affords ToMZnH and ROOSiR3'.
Conversion of a zinc disilazide to a zinc hydride mediated by LiCl
Mukherjee, Debabrata,Ellern, Arkady,Sadow, Aaron D.
, p. 7582 - 7583 (2010/07/09)
An unusual β-elimination reaction involving zinc(II) and LiCl is reported. LiCl and a coordinatively saturated disilazido zinc compound form an adduct that contains activated SiH moieties. In THF/toluene mixtures, this adduct is transformed into a zinc hydride and 0.5 equiv. cyclodisilazane. The Li+ and Cl- ions apparently affect the reaction pathway of the disilazido zinc in a synergistic fashion. Thus, the zinc hydride and cyclodisilazane products of formal β-elimination are not observed upon treatment of the zinc disilazide with Cl- or Li+ separately.
