- Vinylmercury Hydrides: Synthesis and Spectroscopic Characterization
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The first vinylmercury hydrides, and among them the parent compound, have been prepared by a chemoselective reduction of the corresponding vinylmercury chlorides with tributylstannane in the presence of a radical inhibitor. These hydrides have been characterized on the basis of their spectral data (1H, 13C, and 199Hg NMR spectroscopy and mass spectrometry). The photoelectron spectra of the ethenylmercury hydride displays bands at 9.79,10.13, 11.41, and 13.20 eV. On the basis of photoelectron spectra and ab initio quantum chemical calculations some (d-p)π interaction between the vinyl π-system and the mercury d-orbitals could be concluded. Vinylmercury hydrides have been condensed and then revaporized in vacuum at low temperature, but they exhibit a very low stability at room temperature even diluted in toluene (τ1/2 ≈ l min); elemental mercury and the corresponding divinylmercury were formed under these conditions.
- Guillemin, Jean-Claude,Bellec, Nathalie,Szetsi, Sandor Kis,Nyulaszi, Laszlo,Veszpremi, Tamas
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p. 6586 - 6591
(2008/10/09)
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- UEBER EINE trans-EINFLUSS-REIHE DER ORGANYLANIONEN AUS 13C-NMR-SPEKTROSKOPISCHEN UNTERSUCHUNGEN VON ORGANYLQUECKSILBERISOBUTYLVERBINDUNGEN
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The 1J(199Hg-13C) coupling constants of isobutylmercury compounds RHgCH2CHMe2 (R=organo group) have been measured and compared to the coupling constants of diisobutylmercury and diorganomercury compounds HgR2.Between the coupling constants 1J(Hg-Ci-Bu) and 1J(Hg-CR), which have been normalized to the coupling constants of the symmetric compounds concerned, a linear relation has been found.This relation, which can be deduced from the Fermi contact term on the basis of the simple hybrid orbital model, shows that the coupling constant 1J(Hg-Ci-Bu) reflects the s-character of the mercury hybrid orbital concerned and accordingly the NMR trans-influence of the organo group R.The NMR trans-influence decreases in the sequence t-Bu > i-Pr ca. cyclo-C6H11 > Et ca. n-Pr ca. n-Bu ca. i-Bu > CH2Ph ca.CH2CH=CH2 ca.Me > CH2SiMe3 > Ph ca.CH=CH2 > CH2SPh > CCl3 > C6Cl5 > CCPh ca.CCH.
- Steinborn, Dirk,Taube, Rudolf,Radeglia, Reiner,Hoebold, Wolfram
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p. 139 - 148
(2007/10/02)
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