DISPLACEMENT OF NORBORNADIENE (NBD) FROM THE MIXED ALKYL COMPOUND, PT(CH3)(CF3)(NBD) BY VARIOUS LIGANDS AND THE INSERTION OF DIFLUOROCARBENE INTO A PT-CH3 BOND PROMOTED BY THE ADDITION OF IODIDE-ION TO PT(CH3)(CF3)(NBD)

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 Pt-CH3 bond. The products were characterized by multinuclear NMR spectroscopy then converted into dppe derivatives, which were separated and isolated.