Displacement of norbornadiene (NBD) from the mixed alkyl compound, Pt(CH3) (CF3)(NBD) by various ligands and the insertion of difluorocarbene into a PtCH3 bond promoted by the addition of iodide ion to Pt(CH3) (CF3)(NBD)

Abstract

Pt(CH3)(CF3)(NBD) was found to react with neutral ligands L to give cis-Pt(CH3)(CF3)L2 (L2 = 1,2-bis(diphenylphosphino)ethane (dppe); 2,2′-dipyridyl (bipy); N,N,N′,N′-tetramethylethylenediamine (tmen); and L = pyridine (py); dimethylsulfoxide-S (DMSO). These reactions occurred less readily than with Pt(CF3)2(NBD). With (CH3CN, cis-Pt(CH3(CF3)(NBD) gave cis-Pt(CH3)-(CF3)(CH3CN)2 in equilibrium with starting materials. N,N-dimethylformamide (DMF) did not react. Pt(CH3)(CF3)(NBD)reacted with iodide to give a mixture of Pt(CH3)I(NBD), Pt(CF3)I(NBD), and Pt(-CF2CH3)I(NBD), the product of a formal insertion of a difluorocarbene moiety into a PtCH3 bond. The products were characterized by multinuclear NMR spectroscopy then converted into dppe derivatives, which were separated and isolated.