The reaction of $C_{60}$ with $Re_3(μ-H)_3(CO)_{11}(NCMe)$ in refluxing chlorobenzene produces $Re_3(μ-H)_3(CO)_9(μ_3-η^2η^2η^2-C_{60})$ (1). Initial decarbonylation of 1 with $Me_3NO/MeCN$ followed by reaction with $PPh_3$ in boiling chlorobenzene affords $Re_3(μ-H)_3(CO)_8(PPh_3)(μ_3-η^2η^2η^2-C_{60})$ (2). Treatment o 1 with $Ph_3P=NCH_2Ph$ at room temperature gives a benzyl isocyanide substituted product $Re_3(μ-H)_3(CO)_8(PhCH_2NC)(μ_3-η^2η^2η^2-C_{60})$ (3). Compound 1, 2, and 3 have been isolated as crystalline solids and characterized by spectroscopic (infrared, mass, $^1H$, $^31P$, and $^13C$ NMR) and analytical data. The structure of 3 has been determined by a single-crystal X-ray diffraction study. The $C_60$ ligand is coordinated to the trirhenium triangle in a $μ_3-η^2η^2η^2$ bonding mode, and the benzyl isocyanide ligand occupies an axial position of a rhenium atom. Electrochemical properties of 1 and 2 have been studied by cyclic voltammetry (CV) in chlorobenzene (CB) solutions. The general features of CV curves have revealed four reversible redox couples for 1 and2 in the CB potential window. The CV results suggest that a $C_60$-mediated electron transfer to the trirhenium center takes place in $1^{2-}$ species for 1 and $2^{3-}$ for 2.
