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

Alkali metal dihydrogen‐antimonides [M(L)( x )SbH(2)], 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 )SbH(2)] was the appropriate starting compound for the synthesis of the first primary silylstibane (Me(3)Si)(3)SiSbH(2) (3) which was characterized by NMR and IR spectroscopy. Reaction of 3 with (Dipp(2)NacNac)Ga (Dipp(2)NacNac=HC{C(Me)N(Dipp)}(2); Dipp=2,6‐iPr(2)C(6)H(3)) resulted in the formation of (Dipp(2)NacNac)GaH(SbHSi(SiMe(3))(3)) (4) which was furthermore characterized by single crystal x‐ray diffraction.