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).

f-Element Zintl Chemistry: Actinide-Mediated Dehydrocoupling of HSb Affords the Trithorium and Triuranium Undeca-Antimontriide Zintl Clusters [{An(Tren)}(μ-Sb)] (An = Th, U; Tren = {N(CHCHNSiPr)}).

Reaction of the cesium antimonide complex [Cs(18C6)][SbH] (, 18C6 = 18-crown-6 ether) with the triamidoamine actinide separated ion pairs [An(Tren)(L)][BPh] (Tren = {N(CHCHNSiPr)}; An/L = Th/DME (); U/THF ()) affords the triactinide undeca-antimontriide Zintl clusters [{An(Tren)}(μ-Sb)] (An = Th (), U ()) by dehydrocoupling. Clusters and provide two new examples of the Sb Zintl trianion and are unprecedented examples of molecular Sb being coordinated to anything since all previous reports featured isolated Sb Zintl trianions in separated ion quadruple formulations with noncoordinating cations. Quantum chemical calculations describe dominant ionic An-Sb interactions in and , though the data suggest that the latter exhibits slightly more covalent An-Sb linkages than the former.

Thorium(IV)-antimony complexes exhibiting single, double, and triple polar covalent metal-metal bonds.

There is continued burgeoning interest in metal-metal multiple bonding to further our understanding of chemical bonding across the periodic table. However, although polar covalent metal-metal multiple bonding is well known for the d and p blocks, it is relatively underdeveloped for actinides. Homometallic examples are found in spectroscopic or fullerene-confined species, and heterometallic variants exhibiting a polar covalent σ bond supplemented by up to two dative π bonds are more prevalent.

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.

Binary interpnictogen compounds bearing diaryl bismuth fragments bound to all lighter pnictogens.

Multiple interpnictogen compounds with covalent single bonds between a diarylbismuth fragment and all lighter pnictogens were prepared from the corresponding diarylhalido bismuthanes. The aminobismuthanes PhBiNMe (1) and MesBiNMe (2) (Mes = 2,4,6-trimethylphenyl-) have been obtained a salt metathesis reaction and compound 2 was successfully reacted with BuNH in a condensation reaction to yield MesBiNHBu (3). The bismuthanyl phosphanes ArBiPBu (Ar = Ph: 4 and Ar = Mes: 5) and arsanes ArBiAsBu (Ar = Ph: 8 and Ar = Mes: 9) were also obtained salt metathesis.