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Coordination of alkenes at a highly electrophilic site. New dicationic platinum(II) complexes: Synthesis, structure, and reactions with nucleophiles

TitleCoordination of alkenes at a highly electrophilic site. New dicationic platinum(II) complexes: Synthesis, structure, and reactions with nucleophiles
Publication TypeArticolo su Rivista peer-reviewed
Year of Publication2002
AuthorsHahn, C., Morvillo Pasquale, Herdtweck E., and Vitagliano A.
JournalOrganometallics
Volume21
Pagination1807-1818
ISSN02767333
KeywordsComplexation, 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.

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URLhttps://www.scopus.com/inward/record.uri?eid=2-s2.0-0009828068&doi=10.1021%2fom010833d&partnerID=40&md5=714fcd7acbc32f284dfeb8f7d3618d47
DOI10.1021/om010833d
Citation KeyHahn20021807