| Title | Coordination of alkenes at a highly electrophilic site. New dicationic platinum(II) complexes: Synthesis, structure, and reactions with nucleophiles |
|---|---|
| Publication Type | Articolo su Rivista peer-reviewed |
| Year of Publication | 2002 |
| Authors | Hahn, C., Morvillo Pasquale, Herdtweck E., and Vitagliano A. |
| Journal | Organometallics |
| Volume | 21 |
| Pagination | 1807-1818 |
| ISSN | 02767333 |
| Keywords | Complexation, Complexes, Decomposition, Molecular Structure, Olefins, Organometallics, Platinum, Synthesis (chemical), X ray diffraction analysis |
| Abstract | Dicationic platinum(II) alkene complexes [Pt(PNP)(alkene)](BF4)2 (alkene = ethylene, propene, 1-butene, Z- and E-2-butene, styrene, norbornene; PNP = 2,6-bis(diphenylphos-phinomethyl)pyridine) have been prepared and characterized by 1H and 13C NMR spectroscopy, and the molecular structure of the ethylene complex has been determined by X-ray diffraction analysis. Nucleophilic attack at the coordinated double bond takes place more readily than for known neutral and monocationic species, and a variety of protic nucleophiles NuH (MeOH, H2O, aromatic amines) give the corresponding β-functionalized σ-alkyl complexes [Pt(PNP)(CHRCHR′Nu)]BF4 also in the absence of auxiliary bases. In the case of the styrene derivatives an unusual decomposition pathway gives the stable alkenyl complex [Pt(PNP)(CH=CHPh)]BF4. A competitive equilibrium process between substitution and addition was revealed by reacting ethylene with the isolated aniline complex [Pt(PNP)(PhNH2)](BF4)2. The nucleophilic addition product was found to be thermodynamically favored over the substitution product more than in the case of the analogous palladium complexes. |
| Notes | cited By 56 |
| URL | https://www.scopus.com/inward/record.uri?eid=2-s2.0-0009828068&doi=10.1021%2fom010833d&partnerID=40&md5=714fcd7acbc32f284dfeb8f7d3618d47 |
| DOI | 10.1021/om010833d |
| Citation Key | Hahn20021807 |
