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Issue 13, 2007
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Electrochemistry and [60]fullerene displacement reactions of (dihapto-[60]fullerene) pentacarbonyl metal(0) (M = Cr, Mo, W)

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Abstract

Cyclic voltammetry (CV) measurements on (η2-C60)M(CO)5 complexes (M = Cr, Mo, W) in dichloromethane show three [60]fullerene-centered and reversible reduction/oxidation waves. The E1/2 values of these waves are shifted to positive values relative to the corresponding values of the uncoordinated [60]fullerene in the same solvent. A Jahn–Teller type distortion of the spherical surface of [60]fullerene promoted by [60]fullerene–metal π-backbonding may explain the observed positive shifts. Lewis bases (L = piperidine and triphenyl phosphine) displace [60]fullerene from (η2-C60)M(CO)5 complexes. Analysis of the activation parameters for the metal–[60]fullerene dissociation, the metal–[60]fullerene bond enthalpies (from DFT computations), and metal–solvent (benzene) bond enthalpies (from DFT computations) suggests appreciable solvent contribution to the transition state leading to formation of the intermediate species solvent–M(CO)5. Appreciable transition state stabilization due to solvation of the intermediate species is inferred for M = Mo and W. For M = Cr, stabilization of the intermediate species due to solvation is not accompanied by the corresponding transition state stabilization.

Graphical abstract: Electrochemistry and [60]fullerene displacement reactions of (dihapto-[60]fullerene) pentacarbonyl metal(0) (M = Cr, Mo, W)

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Publication details

The article was received on 14 Dec 2006, accepted on 31 Jan 2007 and first published on 09 Feb 2007


Article type: Paper
DOI: 10.1039/B618260G
Citation: Dalton Trans., 2007,0, 1293-1299
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    Electrochemistry and [60]fullerene displacement reactions of (dihapto-[60]fullerene) pentacarbonyl metal(0) (M = Cr, Mo, W)

    E. Igartúa-Nieves, Y. Ocasio-Delgado, M. D. L. A. Torres-Castillo, O. Rivera-Betancourt, J. A. Rivera-Pagán, D. Rodriguez, G. E. López and J. E. Cortés-Figueroa, Dalton Trans., 2007, 0, 1293
    DOI: 10.1039/B618260G

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