Synthetic and Structural Studies on the Transition-Metal Fullerene Complexes (η<sup>2</sup>-C<sub>60</sub>)M[(η<sup>5</sup>-Ph<sub>2</sub>PC<sub>5</sub>H<sub>4</sub>)<sub>2</sub>Ru] and (η<sup>2</sup>-C<sub>60</sub>)M[(η<sup>5</sup>-Ph<sub>2</sub>PC<sub>5</sub>H<sub>4</sub>)<sub>2</sub>Co]<sup>+</s
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A toluene solution of C60 reacted with an equimolar quantity of M(dba)2 (M = Pd, Pt; dba = dibenzylideneacetone) and (η5-Ph2PC5H4)2Ru or with M(PPh3)4and (η5-Ph2PC5H4)2Ru at room temperature to give the dinuclear transition-metal fullerene complexes (η2-C60)M[(η5-Ph2PC5H4)2Ru] (1, M = Pd; 2, M = Pt), whereas the o-dichlorobenzene solution of C60 reacted with an equimolar amount of M(dba)2 and [(η5-Ph2PC5H4)2Co]+(PF6)- or with M(PPh3)4 and [(η5-Ph2PC5H4)2Co]+(PF6)- under similar conditions to afford the dinuclear transition-metal fullerene complexes (η2-C60)M[(η5-Ph2PC5H4)2Co]+(PF6)- (3, M = Pd; 4, M = Pt). In addition, the related complex {[η5-Ph2P(O)C5H4]2Co}+(PF6)- (5) was prepared by oxidation of [(η5-Ph2PC5H4)2Co]+(PF6)- with an excess amount of aqueous peracetic acid in acetone at room temperature. While 1−4 are the first examples of neutral and cationic dinuclear M/Ru and M/Co (M = Pd, Pt) fullerene complexes, 5 is the first organocobalt Cp complex containing a phosphoryl substituent. All products 1−5 have been fully characterized by elemental analysis, spectroscopy, and X-ray crystal diffraction techniques and, for 1 and 2, by cyclic voltammetry.
