428872-97-3Relevant academic research and scientific papers
Coordination of alkenes at a highly electrophilic site. New dicationic platinum(II) complexes: Synthesis, structure, and reactions with nucleophiles
Hahn, Christine,Morvillo, Pasquale,Herdtweck, Eberhardt,Vitagliano, Aldo
, p. 1807 - 1818 (2002)
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.
