The molecular and electronic structure of M(η3-C3H5)2 (M = Ni, Pd, Pt) has been investigated by means of quasi-relativistic gradient-corrected density functional calculations. Geometries have been ...fully optimized by considering both trans and cis arrangements of the bis(η3-allyl) moiety. Binding energy differences between isomers are always smaller than 0.2 kcal/mol; in particular, cis-Ni(η3-C3H5)2 is computed to be more stable than trans-Ni(η3-C3H5)2, while a reversed order is obtained for Pd and Pt analogues. Computed geometrical parameters of trans-Ni(η3-C3H5)2 compare very well with available structural data. Moreover, a new assignment of variable energy photoelectron spectroscopy measurements Li, X.; Bancroft, G. M.; Puddephatt, R. J.; Liu, Z. F.; Hu, Y. F.; Tan, K. H. J. Am. Chem. Soc. 1994, 116, 9543−9554 is proposed by assuming that the trans:cis ratio in the gas phase is close to one.
Gut beschirmte MOFs: Eine neue Serie von hydrophoben isoretikulären porösen Zirconiumoxid‐Dicarboxylat‐MOFs wurde entwickelt (siehe Bild, Zr blaue Polyeder, O rot, C schwarz). Die Materialien ...zeichnen sich durch ein eindimensionales Porensystem, eine seltene Kombination von Lewis‐Acidität und hydrophobem Charakter sowie eine höhere hydrothermische und mechanische Stabilität als ihre polymorphen UiO‐MOF‐Gegenstücke aus.
The molecular and electronic structure of hexakisμ-(dimethylarsinodithioate-S:S‘)-μ4-thioxotetrazinc has been investigated by combining X-ray diffraction measurements, electrospray mass spectrometry ...(ESI), UV absorption spectroscopy, and density functional calculations. The polynuclear zinc complex consists of discrete “tetrazinc sulfide” moieties held together by van der Waals interactions. The unit cell contains four independent molecules and four solvent molecules. Each independent unit is characterized by a central μ4-S coordinated to four Zn ions, each of them at the center of an irregular tetrahedron of S atoms. ESI measurements point out that the synthesis of the analogous Cd derivative was successful. Crystal data are as follows: chemical formula, C12H36As6Cl1.5S13Zn4; monoclinic space group P21/n (no. 14); a = 30.4228(7) Å, b = 18.3720(5) Å, c = 32.3758(8) Å, β = 95.857(1)°; Z = 16. Theoretical calculations indicate that, despite their structural arrangement, neither the Zn nor the Cd complex can be considered molecular models of the extended ZnS and CdS. Nevertheless, the electronic transitions localized in the Zn4(μ4-S) and Cd4(μ4-S) inner cores of the title compounds have the same nature as those giving rise to the maxima in the excitation spectra of the extended Zn4S(BO2)6 and Cd4S(AlO2)6 Blasse, G.; Dirksen, G. J.; Brenchley, M. E.; Weller, M. T. Chem. Phys. Lett. 1995, 234, 177.
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