Alkali metal oxides trapped by diethylzinc

Abstract

Reactions of alkali metal hydroxides with neat diethyl zinc lead to the formation of oxo-centered clusters M2O(ZnEt2)n (M = Na, n = 3 or M = K, Rb, n = 4). These molecules crystallize in highly symmetric space groups, forming extended structures supported by weak M-H interactions. We discuss the mechanistic implications and relationship of these structures to known (oxo)organozincates.

Structure of a pentamanganese(II)–phenoxide cluster with a central five-coordinate oxide: MnII 5(μ-OPh)6(μ3-OPh)2(μ5-O)(Py)6·Py (Py is pyridine)

“…Cole et al, 2002;Chandrasekhar et al, 2014;Mehring et al, 2006;Cabeza et al, 2006;Kondaveeti et al, 2012). Several pentanuclear clusters with metal atoms situated about a single central trigonal bipyramidal oxide, although with different overall structures from the present report, are worthy of note (Zane Miller et al, 2014;Kang et al, 2007;Williams & White, 2007;Henderson et al, 1994;Glatz et al, 2009;Graser et al, 2013;Aspinall & Tillotson, 1996). Based on a search of the Cambridge Structure Database (Groom et al, 2016), three pentanuclear clusters with analogous core geometry to ours have been reported.…”

Alkali-Metal-Mediated Synergistic Effects in Polar Main Group Organometallic Chemistry

“…Since Et 2 Zn is a volatile liquid, it can be used neat in reactions. Refluxing it with sodium hydroxide had a surprising outcome in producing the disodium trizinc oxo-centered cluster [Na 2 (ZnEt 2 ) 3 ­(μ 5 -O)] ( 197 ) . A mechanism has been proposed in which two molecules of initially formed EtZnONa lose ZnO to form Na 2 OZnEt 2 , which picks up two molecules of Et 2 Zn to form the isolated product (Scheme ).…”

“…Refluxing it with sodium hydroxide had a surprising outcome in producing the disodium trizinc oxo-centered cluster [Na 2 (ZnEt 2 ) 3 (μ 5 -O)] (197). 224 A mechanism has been proposed in which two molecules of initially formed EtZnONa lose ZnO to form Na 2 OZnEt 2 , which picks up two molecules of Et 2 Zn to form the isolated product (Scheme 125). Together with the heavier alkali metal congeners, M 2 (ZnEt 2 ) 4 (μ 6 -O) (M = K, 198; or Rb, 199), this sodium−zinc species belongs to a set of compounds with extended structures comprising highly symmetric crystal-packing motifs supported by intercluster interactions between the alkali metal ions and H atoms of the ethyl groups.…”

Ring Opening Polymerization of L-Lactide With Two Different Zinc(ii) Phenoxy-Imine Complexes as Initiators

“…Complex C1 was prepared according to a procedure described in the literature with some modifications. [26][27][28][29][30][31] In a 25 mL Schlenk tube, ZnEt 2 (15 wt% solution in hexane) (1.46 mL, 1.78 mmol) was slowly added to a solution of L1 (0.50 g, 1.78 mmol) in dry toluene (15 mL). The reaction mixture was stirred overnight at room temperature.…”