Functionalization of [60]fullerene using organometallic complexes and amines.

摘要

The organometallic functionalization of C60 can produce novel materials with potential applications in fields such as material science, electronics, and catalysis.[1] Understanding the structure-dependent electronic and mechanical properties of C60 is critical for their chemical manipulations and technological applications.;The reactions of C60 with primary and secondary amines [2-4] produce adducts that can be precursors of active catalysts. They react to form tetra(amino)-fullerene epoxide (amino=piperidine). The progress of adduct formation was followed by monitoring the increase of the absorbance values at 407 nm under flooding conditions where the piperidine concentration is greater than the concentration of C60 ([pip][C 60]). Plots of absorbance versus time were biexponential, indicative of consecutive first order reactions. The first segment of the biphasic plot was ascribed to two consecutive piperidine additions. The second segment of the biphasic plot was ascribed to another two consecutive piperidine additions. The reaction corresponding to the second segment was followed by a hydrogen peroxide epoxidation producing a tetra(amino)-fullerene epoxide. Also, we are reporting the mechanisms of C60 dissociation from (eta2-C60)Ir(CO)(PPh3)2Cl. The dissociation was followed observing the decrease of the absorbance values at 550 nm. Plots of absorbance versus time were exponential. Two mechanisms of reaction are being proposed. One of the proposed mechanisms may involve solvent-assisted C60 dissociation. The order with respect to non-coordinating solvents and to coordinating solvent is zero and first order, respectively. The rate constant values for the dissociation are independent of the C60 concentration.