Heterometallic binuclear complexes involving the mercury-platinum bond as a source of a platinum carbenoid in reactions with fullerene-60

Article abstract of DOI:10.1007/BF01558083

The cleavage of two ?-bond and the formation of a metallocomplex, (η²-C60)Pt(PPh3)2, occur in a new reaction between fullerene-60 and binuclear heterometallic compounds having a mercury-platinum bond (retro-insertion promoted by C60).One of these, trans-Ph2CHCH2HgPt(PPh3)2Br, 1, which contains an electron-donating group at the mercury atom, reacts two orders of magnitude faster than cis-(CF3)2CFHgPt(PPh3)2CH=CPh2, 2, which has an electron-withdrawing substituent at mercury.An asymmetrical organomercury compound is the second product of the reaction.The reactants and products have been characterized by spectroscopic data (1H, 31P 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 C60.The platinum-fullerenyl radical cis-C*60Pt(PPh3)2R² was identified by ESR spectroscopy. - Key words: metallocomplexes; fullerene-60; heterometallic compounds; mercury-platinum bond, retro-insertion; Pt-centered free radical; ESR, NMR, UV-VIS, spectra.