Complexation and activation of the bisfulleroid C64H4 with triosmium carbonyl clusters

Reaction of C64H4 (1) and Os3(CO)10(NCMe)2 in refluxing chlorobenzene affords (μ-H)Os3(CO)9(μ,η4-C64H3) (2) and Os(CO)3(η4-C64H4) (3). Compound 2 apparently arises from C–H bond activation of 1 to generate an η4-dienyl motif. In contrast, compound 3 is produced by insertion of one osmium atom into a pentagonal ring of 1, together with the Os3 cluster fragmentation. Complexes 2 and 3 have been characterized by IR, NMR, and mass spectroscopies. The structure of 3·C7H8 was determined by a single-crystal X-ray diffraction study.

Graphical abstractReaction of C64H4 and Os3(CO)10(NCMe)2 results in a C–H bond activation to give (μ-H)Os3(CO)9(μ,η4-C64H3) and a C–C bond activation to give Os(CO)3(η4-C64H4).Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► The bisfulleroid C64H4 can bind Os3 clusters through the ethylene group. ► C–H activation of C64H4 with Os3 cluster produces a hydrido-dienyl complex. ► The Os atom can insert into one five-membered ring of C64H4 molecule. ► A large orifice has been generated on the fullerene core.