Synthesis of Lewis Acid-Base Adducts Between Potassium Dihydrogenpnictogenides and Group 13 Lewis Acids.

Lewis acid-base adducts between potassium dihydrogenpnictogenides [K(18c6)PnH] (Pn=P, As) and Trialkylgallanes (GaMe, GaEt, GatBu) as well as BH were synthesized. In the course of these investigations, we were able to fully characterize a row of compounds of the type [K(18c6)(thf)][PnH(ER)] (E=B: R=H; E=Ga: R=Me, Et, tBu). Based on the successful syntheses of these species, we also synthesized several compounds of the composition [K(18c6)(thf)][Pn(SiMe)(ER)] (n=1, 2) starting from [KPn(SiMe)] (Pn=P and As) and ER (E=B, Al, In: R=Me; E=Ga: R=Me, Et, tBu).

Formation and Reactivity of heavy Group 14-15 bonds.

A series of low-valent Group 14-15 compounds were obtained starting from [(Dipp NacNac)MCl] (M=Ge-Pb) (I-III) (Dipp NacNac=HC{C(Me)N(Dipp)} ) and M'E(SiMe ) (M'=Li, E=As; M'=K, E=Sb, Bi) (IV-VI). In the course of this investigations we were able to fully characterize all permutations except Pb-Bi for compounds of the composition [(Dipp NacNac)ME(SiMe ) ] (1 : M=Ge, 2 : M=Sn, 3 : M=Pb). Thus, we report the first low valent tetrelene with Sn-Bi bond.

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

Alkali metal dihydrogen-antimonides [M(L) SbH ], 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) SbH ] was the appropriate starting compound for the synthesis of the first primary silylstibane (Me Si) SiSbH (3) which was characterized by NMR and IR spectroscopy.

Construction of Inorganic Crown Ethers by s-Block-Metal-Templated Si-O Bond Activation.

We herein report the synthesis, structures, coordination ability, and mechanism of formation of silicon analogs of crown ethers. An oligomerization of D (I) ( D ,=(Me Si O) ) was achieved by the reaction with GaI and MI (M=Li, Na, Mg, Ca, Sr). In these reactions the metal cations serve as template and the anions (I /[GaI ] ) are required as nucleophiles.

Coordination polymers of alkali metal cyclosiloxazanides with one- and two-dimensional structures.

The reaction of O(SiMeCl) with ammonia yielded the cyclic siloxazane O(SiMe)NH (1), which was used as a precursor for the synthesis of siloxazanide-type alkali metal salts. The metalation of 1 with the strong bases BzA (A = Na, K, Rb, Cs and Bz = benzyl) results in different dimensional structures depending on the alkali metal ion used. These results give new insights into framework design with inorganic building blocks and the coordination ability of siloxanes.