| Title | Olefins coordinated at a highly electrophilic site - Dicationic palladium(II) complexes and their equilibrium reactions with nucleophiles |
|---|---|
| Publication Type | Articolo su Rivista peer-reviewed |
| Year of Publication | 2001 |
| Authors | Hahn, C., Morvillo Pasquale, and Vitagliano A. |
| Journal | European Journal of Inorganic Chemistry |
| Pagination | 419-429 |
| ISSN | 14341948 |
| Keywords | 2, 2 butene, 6 bis(diphenylphosphanylmethyl)pyridine, aliphatic amine, alkene derivative, aromatic amine, article, chemical binding, chemical reaction, chemical structure, complex formation, electron transport, Ethylene, norbornene derivative, Nuclear magnetic resonance spectroscopy, palladium complex, propylene, pyridine derivative, Reaction analysis, structure analysis, styrene, synthesis, unclassified drug |
| Abstract | Dicationic olefin palladium(II) complexes [Pd(PNP)(olefin)] (BF4)2 [olefin = ethylene, propene, styrene, (Z)-2-butene, (E)-2-butene, norbornene; PNP = 2,6-bis(diphenylphosphanylmethyl)pyridine] have been prepared and characterized by 1H, 13C, and 31p NMR spectroscopy. The coordinated double bond in these complexes is strongly electrophilic, and easily adds a variety of nucleophiles NuH (H2O, MeOH, aliphatic and aromatic amines). This reaction competes with olefin displacement in a rapidly reversible equilibrium process, as a result of which the addition products can also be obtained starting from the substituted compounds [Pd(PNP)(NuH)](BF4)2 and the appropriate olefin. Equilibrium constants for the addition and substitution reactions have been determined in a number of cases. Proton abstraction from [Pd(PNP)(CHRCHR′NuH)]2+ by NaHCO3 quantitatively drives the equilibrium to β-functionalized alkyl complexes of the general formula [Pd(PNP)(CHRCHR′Nu)](BF4), which are unusually stable to β-H elimination. |
| Notes | cited By 49 |
| URL | https://www.scopus.com/inward/record.uri?eid=2-s2.0-0035146462&partnerID=40&md5=42bbc5fe8aaad1ea54adc148850b917f |
| Citation Key | Hahn2001419 |
