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Chalcogenide Exchange Reaction of [RGa(μ3-Te)]4 with Elemental Sulfur and Selenium: A Density Functional Theory Study

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Abstract

Thermodynamic and mechanistic features of the chalcogen exchange reaction between [RGa(μ 3-Te)]4 and elemental sulfur or selenium have been studied employing density functional theory (DFT) calculations using the BL3YP basis set and Stuttgart pseudopotentials. For [MeGa(μ 3-E)]4 (E=S, Se, Te) the correlation between the calculated parameters and diffraction data for their isolable analogs is greater than 98%. Each step of the conversion of [MeGa(μ 3-Te)]4 to [MeGa(μ 3-E)]4 via [Me4Ga4(μ 3-Te)4−x (μ 3-E) x ] (E=S, Se) is predicted to occur as a series of isolated reactions. The entropy change for each chalcogen exchange is small in magnitude and corresponds to the degree of cage distortion within the cubane molecules. Calculations performed on [MeGa(μ 3-Te)]4...S8 and [MeGa(μ 3-Te)]4-S suggest that an increase in electrophilicity of the gallium next to a surface bound tellurium may result in nucleophilic cage opening for which intermediate structures are calculated.

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Authors and Affiliations

  1. Department of Chemistry and Center for Nanoscale Science and Technology, Rice University, Houston, Texas, 77005

    Bradley D. Fahlman, Andrew D. Daniels, Gustavo E. Scuseria & Andrew R. Barron

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  1. Bradley D. Fahlman
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  2. Andrew D. Daniels
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  3. Gustavo E. Scuseria
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  4. Andrew R. Barron
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Correspondence to Andrew R. Barron.

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Fahlman, B.D., Daniels, A.D., Scuseria, G.E. et al. Chalcogenide Exchange Reaction of [RGa(μ3-Te)]4 with Elemental Sulfur and Selenium: A Density Functional Theory Study. Journal of Cluster Science 13, 587–599 (2002). https://doi.org/10.1023/A:1021135930768

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