Quantum chemical calculations of the anions AeF- (Ae = Be - Ba) and the isoelectronic group-13 molecules EF (E = B - Tl) have been carried out using ab initio...

We report herein the synthesis of a stable plumbylone (3) by reduction of a bromodigermylplumbylene (2) with 2.2 equiv of potassium graphite (KC 8 ). The molecular structure of 3 was established by a singlecrystal X-ray diffraction study and features a twocoordinated Pb center with an acute GeÀ PbÀ Ge bond angle. Computational studies showed that this complex (3) possesses a singlet electronic ground state with a Pb 0 center. Its high thermal stability can be most likely ascribed to the delocalization of π electrons over the GeÀ PbÀ Ge moiety. A preliminary reactivity study demonstrates that complex 3 can deliver Pb 0 atoms to an organic azide producing a tetrameric imido complex [(PbNDipp) 4 ] (Dipp = 2,6-i Pr-C 6 H 3 , 4) and perform a metathesis reaction with GeCl 2 •dioxane to produce a bis(germylene)-stabilized germylone (5), highlighting the synthetic utility of 3.

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Monovalent group 15 cations L2Pn + (L = σ-donor ligands, Pn = N, P, As, Sb, Bi) have attracted significant experimental and theoretical interest because of their unusual electronic structures and growing synthetic potential. Herein, we describe the synthesis of a family of antimony(I) and bismuth(I) cations supported by a bis(silylene) ligand [(TBDSi2)Pn][BArF4] (TBD = 1, 8, 10, 9-triazaboradecalin; ArF = 3,5-CF3-C6H3; Pn = Sb, (2); Bi, (3)). The structures of 2 and 3 have been unambiguously characterized spectroscopically and by X-ray diffraction analysis and DFT calculations. They feature bis-coordinated Sb and Bi atoms which exhibit two lone pairs of electrons. The reactions of 2 and 3 with methyl trifluoromethane sulfonate provide a approach for the preparation of dicationic antimony(III) and bismuth(III) methyl complexes. Compounds 2 and 3 serve as 2e donors to group 6 metals (Cr, Mo), giving rise to ionic antimony and bismuth metal carbonyl complexes 6–9.