Bis(carbazolide) complexes M[3,6-tBu -1,8-(RC≡C) Carb] (THF) (R=SiMe , n=0, M=Ca, Yb; R=Ph, n=1, M=Ca, Yb; n=0, M=Yb) were synthesized through transamination reaction of M[N(SiMe ) ] (THF) with two molar equivalents of carbazoles. The complexes feature M(η -C≡C) structural motif composed of M(II) ions encapsulated by four acetylene fragments due to atypical for alkaline- and rare-earth metals η -interactions with triple C≡C bond. This interaction is evidenced experimentally by X-ray diffraction, Raman spectroscopy in the solid state and by NMR-spectroscopy in the solution.
View Article and Find Full Text PDFThis paper submits experimental results of a study directed towards the formation of Eu ions' luminescent centers in CVD diamond films. A new approach is based on use of diamond nanoparticles with a surface modified with Eu ions for seeding at CVD growth. Nanocrystalline diamond films (NCD) doped with Eu have been grown from the gas phase on silicon substrates by microwave plasma-assisted CVD at a frequency of 2.
View Article and Find Full Text PDFA series of benzannulated N-heterocyclic compounds containing divalent 14 group atoms, CH(NR)E, E = C, Si, Ge, Sn, Pb, have been studied by various experimental (vibrational and UV-vis spectroscopy) and theoretical (NICS, ISE, ACID) techniques. The methods used confirm 10 π-electron delocalization (aromaticity) in these heterocycles, however, the aromaticity sequences estimated by the criteria based on different physical properties do not coincide.
View Article and Find Full Text PDFSublimation of sulflower, octathio[8]circulene C 16S 8 ( 1), on heating under high vacuum ( approximately 10 (-5) Torr) leads to successive formation of two modifications: a white film ( 1W) and a red polycrystalline solid ( 1R). When kept at room temperature for several weeks, 1W spontaneously turns pink, reflecting the monotropic phase transition 1W --> 1R. The accurate molecular and crystal structure of 1R has been studied using low-temperature (100 K) high-resolution single crystal X-ray analysis.
View Article and Find Full Text PDFA new trioxystannate-transition metal complex, {[Li][(Me(2)NCH(2)CH(2)O)(3)Sn-Fe(CO)(4)]}(2) (3), exhibiting an unusual type of the heteronuclear bonding between heavier Group 14 elements and transition metals, has been synthesised and completely characterised by NMR, Raman and IR spectroscopy in solution as well as by Raman spectroscopy and X-ray diffraction analysis in the solid state.
View Article and Find Full Text PDFEquatorial-axial isomerism of the tin(II)-iron(0) complex (Me2NCH2CH2O)2Sn-Fe(CO)4 (), which indicates that the free Sn(OCH2CH2NMe2)2 () ligand can behave as a stannylene, has been revealed and studied by NMR and IR spectroscopy in solution as well as by Raman spectroscopy and X-ray diffraction analysis in the solid-state.
View Article and Find Full Text PDFFor the stable germylene, N,N'-di-tert-butyl-1,3-diaza-2-germacyclopent-4-en-2-ylidene, 2, the Raman line for the cyclic C=C stretching mode is strongly enhanced and shifted to longer wavelength, compared with that in reference compounds. The enhancement and frequency shift are even greater than those found for the corresponding stable silylene 1. These results, along with NMR evidence and theoretical calculations, suggest that the aromatic electron delocalization is even greater in the germylene than that in the silylene.
View Article and Find Full Text PDFSpectrochim Acta A Mol Biomol Spectrosc
March 2004
The UV-Vis, pre-resonance Raman and IR spectra of the complex (Cy3P)2Pt=SiMes2 (1) were obtained as well as Raman spectra of some model compounds. The experimental data and the results of normal coordinate calculations show that the stretching vibration of the Si?Pt bond in 1 is not localized, the nuSi=Pt internal coordinate makes significant contribution to two normal modes with frequencies at 465 and 612cm-1, whose Raman intensity is enhanced by pre-resonance.
View Article and Find Full Text PDFNew stereoregular cyclic polysilanols of the general formula [PhSi(O)OH]n (n = 6 and 12) have been selectively obtained in high yields by the reaction of cagelike oligophenylmetallasiloxanes with dilute solutions of hydrochloric acid at low temperatures. An alternative method was used to prepare cis-[PhSi(O)OH](4) from sodium phenylsiloxanolate, cis-[(Na(+))(4)[PhSi(O)O(-)](4)].(1-butanol)(x).
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