HETEROMETALLIC BINUCLEAR COMPLEXES INVOLVING THE MERCURY-PLATINUM BOND AS A SOURCE OF A PLATINUM CARBENOID IN REACTIONS WITH FULLERENE-60

The cleavage of two sigma-bonds and the formation of a metallocomplex, (eta(2)-C-60)pt(PPh(3))(2), occur in a new reaction between fullerene -60 and binuclear heterometallic compounds having a mercury-platinum b ond (retro-insertion promoted by C-60). One Of these; trans-Ph(2)CHCH( 2)HgPt(PPh(3))(2)Br, 1, which contains an electron-donating group at t he mercury atom, reacts two orders of magnitude faster than cis-(CF3)( 2)CFHgPt(PPh(3))(2)CH=CPh(2), 2, which has an electron-withdrawing sub stituent at mercury. An asymmetrical organomercury compound is the sec ond product of the reaction: The reactants and products have been char acterized by spectroscopic data (H-1, P-31 NMR, UV-VIS) and elemental analyses. Compound 2, which is more stable to retro-insertion, gives a Pt-centered free radical upon photolysis. This was used for the free- radical functionalization of C-60. The platinum fullerenyl radical cis -C-60 Pt(PPh(3))(2)R(2) was identified by EPR spectroscopy.