Rearrangement of a σ-2-(Cycloprop-2-enyl)vinyl- to an η3-Cyclopentadienylplatinum(II) Complex. Selective Protonolysis of the Platinum−Methyl Bond

• Published in: Organometallics Vol. 21; no. 24; pp. 5394 - 5400
• Main Authors: Jacob, Volker, Weakley, Timothy J. R, Haley, Michael M
• Format: Journal Article
• Language: English
• Published: American Chemical Society 25.11.2002
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/om0206507

The σ-2-(cycloprop-2-enyl)vinylplatinum(II) complex (PEt3)2Pt(Me)(CHCH-cyclo-C3HPh2) (5) was prepared and characterized by NMR spectroscopy and X-ray crystallography. Treatment of 5 with Bronsted acids results in selective splitting of the Pt−methyl bond to give chloro derivative (PEt3)2Pt(Cl)(CHCH-cyclo-C3HPh2) (6), or the rearranged η3-diphenylcyclopentadienyl cation 7 + , depending on the acid employed. Formation of cation 7 + could also be accomplished by treatment of 6 with TlPF6. Monitoring the protonolysis reactions by NMR spectroscopy at −60 °C, however, showed no evidence for platinabenzene or platinabenzvalene intermediates.