American Chemical Society
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Geometric and Electronic Structures of Os3(CO)93222-C60), Os3(CO)8(P(CH3)3)(μ3222-C60), and Their Anions (Q = −1 to −4): Reduction-Induced Conversion of π to σ C60−Metal Complexes

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journal contribution
posted on 2004-08-02, 00:00 authored by Kyoung Hoon Kim, Jaehoon Jung, Young-Kyu Han
The geometries and electronic structures of Os3(CO)93222-C60) (OsF1), Os3(CO)8(P(CH3)3)(μ3222-C60) (OsF2), and their mono-, di-, tri-, and tetra-anions were calculated using a density functional method. Our calculations show that all three Os atoms are coordinated to C60 in a π-type mode for the mono- and dianions, as well as in the neutral OsF1 and OsF2 complexes, but that third and fourth electron reductions form mixed σ−π-type coordinated compounds. A third electron reduction produces the Os3(CO)93221-C60)3- and Os3(CO)8(P(CH3)3)(μ3221-C60)3- complexes, while a fourth electron reduction produces the Os3(CO)93211-C60)4- and Os3(CO)8(P(CH3)3)(μ3221-C60)4- complexes. Our reduction potentials are calculated, in qualitatively good agreement with experimental data obtained using cyclic voltammetry.