Our previous investigations showed that homolytic reactions of C 60 with a number of perfluoroorganic and organomercury(II) compounds occurring under electron impact (EI) in the ionization chamber (IC) of a mass spectrometer could predict the reactivity of C 60 towards these compounds in solution or solid state. To expand the scope of this statement, C 60 and C 70 have been reacted with ketones RCOR 1 , where R and R 1 are alkyl, aryl, benzyl, and CF 3 , in an IC under EI to yield products of the addition of R · and R 1 · radicals to the fullerenes, paramagnetic ones being stabilized by hydrogen addition and loss. Experimental evidence in support of a mechanism involving homolytic dissociation of ketone molecules via superexcited states to afford these radicals that react with the fullerenes at the IC surface has been obtained. As anticipated, the reactions between C 60 and several ketones conducted in solution under UV irradiation have afforded Me-, Ph-, and CF 3 -derivatives of C 60 . However, some other products have been identified by mass spectrometry and their formation is reasonably explained. When decalin has been employed as a solvent, decalinyl derivatives of the fullerene have been found among the products and the (9-decalinyl)fullerenyl radical has been registered by EPR. Thus, incomplete but reasonable conformity of the results of the reactions of fullerenes with ketones in an IC under EI with those of the reactions of the same reagents in solution under UV irradiation has been demonstrated, and the former results can predict the latter ones to a reasonable extent.

alnszitute of C/wmi~try and Chemical Technolo.gy, Siberian Branch of the Russian Academy ~/Sciences. 42 u/. K. ,$tarksa, 660049 Krasnoyarsk. Russian Federation. Fax: +7 (391 2) 2.] 8658. E-maih root@chem.krasnoyarsk.su #A. N. ,%esmeyanov Inslitute of Organoelemenz Compounds, Russian Academy of Sciences, 2S ul. Vavilova, 117S13 Moscow, Russian Federation. Fax: + 7 (095~ 135 5085.The reaction of Cp(CO)2Mn=C=CHPh (i} with Pd(PPhO-followed by the replacement of the PPh~ ligands by diphosphmes Ph2PICH2)2PPh 2 (dppe) or Ph2P(Ct-t2)3PPh 2 (dppp) (where dppe is bis(diphenylphosphino)ethane and dppp is 1,3-bisr afforded the binuclear complexes CplCO):MnPd(p*C=CHPh)(dppe) (2a) and Cp(CO):MnPd(~t-C=CHPh)(dppp) (2b), respectively. The reactions of 2a and 2b with Fe~(CO) 9 ga~e the trinuctear complex CpMnFe2(~B-C=CHPh)(CO)8 (37. Competitive transmetaHation took the second pathway to yield clusters containing the PdFe 3 and PdFe, cores. Complex 3 was also formed in the thermal reaction of compound I with I=e2{CO), ~. Complex 3 was studied by IR spectroscopy, IH and t3C NMR spectroscopy, massspectrometp/, and X-my diffraction analysis.

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