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A series of bis(phenylacetylido)(porphyrinato) E(IV) (E = Si, Ge, Sn) derivatives were obtained by reacting lithium phenylacetylide with the corresponding bis(chlorido)(porphyrinato) E(IV) precursors. Crystal structure determinations demonstrated that the transcoordinated acetylide ligands deviate from their expected ideal geometry. Density functional theory calculations and comparison of the packing of the molecules among the homologous series of Si(IV), Ge(IV) and Sn(IV) revealed causes for the deviation from the simple valence shell electron pair repulsion model. Fluorescence and phosphorescence of these organometallic group 14 derivatives were studied and the results are compared to the literature-known properties of the related bis(chlorido) (porphyrinato) E(IV) compounds (E = Si, Ge, Sn). The first crystal structure of a porphyrinato Ge(IV) compound with σ-bonded acetylide ligands is reported. [ABSTRACT FROM AUTHOR]

The reaction of dialkyltinhydrides with dialkylzinc results in a tin metal bond formation. Crystal structures of 1,1,1,2,3,3,3-hepta-phenyl-2-(ethylzincio)tristannane *TMEDA 1, 1,1,2,2,3,3,4,4-octaphenyl-1,4-(ethylzincio)tetrastannane*2TMEDA 2, and triphenyl(phenylzincio)stannane*TMEDA 3 could be obtained. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file. GRAPHICAL ABSTRACT[image omitted] [ABSTRACT FROM AUTHOR]

The series of oligogermanes Pri3Ge(GePh2)nGePri3 (n = 0, 2; n = 1, 3; n = 2, 4; n = 3, 5) were prepared by the hydrogermolysis reaction. All four species were characterized by NMR (¹H and 13C) and UV/visible spectroscopy as well by cyclic voltammetry and differential pulse voltammetry. The oligogermanes exhibited a successive red shift in their absorbance maxima as the length of the Ge-Ge chain was increased, and these molecules also became easier to oxidize as the chain length was increased. The X-ray crystal structures of 4 and 5 as well as the trigermane HPh2GeGePh2GePh2H (6) were determined. The pentagermane 5 was shown to be dichroic in the solid state due to the packing of the individual molecules in a columnar fashion in the crystal. Pentagermane 5 is also luminescent in solution, exhibiting an emission maximum at 380 nm. The physical properties of 5, like the hexagermane Pri3Ge(GePh)4GePri3, mimic the properties of the larger polygermane systems. [ABSTRACT FROM AUTHOR]