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

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.

Trapping reactions with highly unstable hydrides of antimony and bismuth.

(Dipp2NacNac)Ga (Dipp2NacNac = HC{C(Me)N(Dipp)}2; Dipp = 2,6-iPr2C6H3) was used as a trapping reagent for the unstable compounds tBuSbH2 and MeBiH2 to yield (Dipp2NacNac)GaH(SbHtBu) (1) and {(Dipp2NacNac)GaH(BiMe)}2 (2). Moreover, its reactions with a row of alkylated or arylated dichloro-bismuthenes resulted in either bridged species or the formation of a dibismuthane.

Stibine as a reagent in molecular chemistry - targeted synthesis of primary and secondary stibanyl-gallanes and their lighter homologues.

The reactions of SbH3 with one or two equivalents of (Dipp2NacNac)Ga (Dipp2NacNac = HC{C(Me)N(Dipp)}2; Dipp = 2,6-iPr2C6H3) yield the primary and secondary stibanes (Dipp2NacNac)GaH(SbH2) (3) and {(Dipp2NacNac)GaH}2(SbH) (5). Their lighter homologs were obtained from the analogous reactions with phosphine and arsine. All compounds were characterized using heteronuclear NMR-spectroscopy, IR-spectroscopy and single-crystal X-ray diffraction.