Unprecedented noradamantane-type compounds [(R(2,3)Ge)(4)Te(5)] (R(2) = CH(2)CH(2)COOH, R(3) = CH(CH(2)COOH)(2)), containing a Ge-Ge bond, yield from reactions of R(2,3)GeCl(3) with Na(2)Te or Li(2)Te in THF, while reactions with R(1)GeCl(3) (R(1) = CMe(2)CH(2)COMe) afford a double-decker-type cage [(R(3)Ge)(4)Te(6)]; by reaction with hydrazine, the latter reacts to the hydrazone functionalized, monomeric anion [(R(4)Ge)Te(2)](-) (R(4) = CMe(2)CH(2)CNNH(2)Me).
The reaction of the carbodiphosphorane Ph3P=C=PPh3 (1) with MeI in the presence of iodine gives the oxidation product (IC(PPh3)2)2I[I3]·(I2)2 (2). In the solid state dimeric units linked by indefinite ···I−···I2···I3−···I2···I−··· chains are found. An additional I···I contact between the cation and the I2 molecule is formed, amounting to 359.23(5) pm. 2 crystallizes in the monoclinic space group P2/c, with the unit cell dimensions a = 2053.9(1), b = 1011.4(1), c = 1889.8(1) pm; β = 105.21(1)° and Z = 4.
A double-decker (DD) type selenidogermanate complex with C=O functionalized organic decoration, [(R 1 Ge 4 )Se 6 ] (1, R 1 = CMe 2 CH 2 COMe), was synthesized by reaction of R 1 GeCl 3 with Na 2 Se, and subsequently underwent a light-induced transformation reaction to yield [Na(thf) 2 ][(RGe IV ) 2 (RGe III )(Ge III Se)Se 5 ] (2). Similar to the observations reported previously for the Sn/S homologue of 1, the * Prof. Dr. S. Dehnen 1663 product comprises a mixed-valence complex with a newly formed Ge-Ge bond. However, different from the transformation of the tin sulfide complex, the selenidogermanate precursor did not produce a paddlewheel-like dimer of the DD type structure, but led to the formation of a noradamantane (NA) type architecture, which has so far been restricted to the Si/Se and Ge/Te elemental combination.
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