SYNTHESIS AND PROPERTIES OF DONOR-FREE BIS(DIFLUOROMETHYL) CADMIUM, (CF2H)(2)CD - NMR SPECTROSCOPIC DETECTION AND STRUCTURE OF TETRAKIS(DIFLUOROMETHYL) CUPRATE(III) AND RELATED-COMPOUNDS

The reaction of CdR(2) (R = Me, Et) with CF2HI has been investigated. Insertion of difluorocarbene into Cd-C bonds with formation of 1,1-dif luoroethyl, 1,1-difluoropropyl and tetrafluoroethyl derivatives is des cribed. Metathesis of CF2HI with CdEt(2) in non-coordinating solvents gives very reactive, unsolvated (CF2H)(2)Cd in quantitative yield. Spe ctroscopic and chemical properties are reported. Adducts have been obt ained by addition of donors such as diglyme or TMEDA. Partial F vs. Cl exchange with acetyl chloride converts the CF2H group to CFHCl deriva tives. Reaction of (CF2H)(2)Cd with CuCl leads to the formation of the rmally unstable (difluoromethyl)copper(I) species, 'Cu(CF2H)' and [Cu( CF2H)(2)](theta). Disproportionation of the cuprate(I) or its oxidatio n by I-2 or O-2 gives the cuprate(III) anion, [Cu-III(CF2H)(4)](theta) , which is stable in water and air. The crystal structure of [PNP][Cu( CF2H)(4)] has been determined. Mixed difluoromethyl/trifluoromethyl cu prates have been prepared from (CF3)(2)Cu(S(2)CNEt(2)) and (CF2H)(2)Cd in order to verify the square-planar arrangement of substituents by N MR spectroscopy. Identification of compounds was achieved by multinucl ear NMR spectra. NMR parameters are discussed.