Synthesis and reactivity of neutral and cationic pentafluorophenyl platinum(I) derivatives

Abstract

The synthesis of [ClPt(µ-dppm)₂Pt(C₆F₅)](1)(dppm = Ph₂PCH₂PPh₂) is described. The Cl ligand in (1) can be replaced by Br, SCN and by neutral ligands (PPh₃, AsPh₃, pyridine, or CO) to give other Pt^I complexes. MeO₂CCCCO₂Me, SO₂, [N₂C₆H₄Me-p]⁺, and H⁺ insert into the Pt–Pt bond to give A-frame Pt^II complexes. SnCl₂, on the contrary, inserts into the Pt–Cl bond to give Pt–SnCl₃ derivatives. t-Butyl isocyanide acts as do other neutral ligands to give cationic complexes [(Bu^tNC)Pt(µ-dppm)₂Pt(C₆F₅)]⁺, whereas CNC₆H₁₁ and CNC₆H₄Me-p lead to insertion, coordination, or both depending on the conditions of the reaction. The products are characterized by i.r. and ¹H, ¹⁹F, and ³¹P n.m.r. spectroscopy.