Synthesis and Application of Alkali Metal Antimonide-A New Approach to Antimony Chemistry

Angew Chem Int Ed Engl. 2022 Dec 23;61(52):e202213098. doi: 10.1002/anie.202213098. Epub 2022 Nov 28.

Abstract

Alkali metal dihydrogen-antimonides [M(L)x SbH2 ], short: alkali metal antimonides (M=Li, Na, K, Rb, Cs; 1: L=pmdta; 2: L=crown-ether), were prepared from stibine and n-Butyllithium, M(hmds) (hmds=hexamethyldisilazane) or MOtBu, respectively. We developed a generally applicable synthesis route for these compounds and the obtained compounds were examined on their stability depending on the alkali metal and stabilizing additives used, whereby the use of appropriate crown-ethers allowed their isolation and characterization at room temperature. Moreover, the 1,4-dioxane adduct [Na(dioxane)x SbH2 ] was the appropriate starting compound for the synthesis of the first primary silylstibane (Me3 Si)3 SiSbH2 (3) which was characterized by NMR and IR spectroscopy. Reaction of 3 with (Dipp2 NacNac)Ga (Dipp2 NacNac=HC{C(Me)N(Dipp)}2 ; Dipp=2,6-iPr2 C6 H3 ) resulted in the formation of (Dipp2 NacNac)GaH(SbHSi(SiMe3 )3 ) (4) which was furthermore characterized by single crystal x-ray diffraction.

Keywords: Alkali Metals; Antimony; Crown-Ethers; Silylstibane; Transfer Reagents.