Molybdenum-mercury bond. NMR (199Hg, 31P, 1H) and IR study on[(C5H5)(CO)2LMoHgZ] (LP(4-X-C6H4)3 (XF, Cl, Me, OMe), P(CH2CH3)3, P(CH2CH2CN)3; ZCl, I, (C5H5)(CO)2LMo) complexes
| Autor: | J. Y. Le Gall, Jean-Yves Salaün, M. M. Kubicki, Roger Pichon, Mercedes Cano, José A. Campo |
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| Rok vydání: | 1992 |
| Předmět: |
chemistry.chemical_classification
Cyclic compound Stereochemistry Chemical shift chemistry.chemical_element Nuclear magnetic resonance spectroscopy Inorganic Chemistry chemistry.chemical_compound Crystallography chemistry Molybdenum Intramolecular force Materials Chemistry Ligand cone angle Physical and Theoretical Chemistry Inorganic compound Phosphine |
| Zdroj: | Inorganica Chimica Acta. 193:207-212 |
| ISSN: | 0020-1693 |
| DOI: | 10.1016/s0020-1693(00)80354-0 |
| Popis: | IR and multinuclear NMR studies, and in particular those of 199Hg NMR, have been carried out on the title molybdenum-mercury bonded complexes of the type Cp(CO)2(phosphine)MoHgZ. It is found that the 199Hg chemical shifts correlate well with the pKa values and with some electronic parameters, like Hammet's σ p or Bartik's FTχ, for para-substituted triphenyl phosphines and for PEt3. Less basic phosphines give rise to a shielding of mercury nuclei. A particular behaviour of P(CH2CH2CN)3 derivatives is ascribed to a possible intramolecular MoPCH2CH2CN → Hg interaction. The 2J(HgP) coupling constants do not exhibit a clear dependence either on the nature of the para-substituent in triarylphosphines or on the pKa values of the phosphorus ligand involved but do show a good linear correlation with the values of Tolman's θ cone angles: the higher the cone angle is, the lower is the coupling constant. |
| Databáze: | OpenAIRE |
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