A force field for MD simulations on rhenium organometallic compounds developed from enthalpy of sublimation and X-ray diffraction measurements

Abstract

The standard (pº = 0.1 MPa) molar enthalpies of sublimation, at 298.15 K, of methyltrioxorhenium(VII), Δ_subH^o_m[CH₃ReO₃] = 70.2±0.4 kJ.mol^-1, and dirhenium decacarbonyl, Δ_subH^o_m[Re₂(CO)₁₀] = 97.4±0.9 kJ.mol^-1, corresponding to well characterized crystalline phases, were determined by Calvet microcalorimetry. These results, along with structural data obtained in this work by single crystal X-ray diffraction for [CH₃ReO₃], or previously reported for [Re₂(CO)₁₀], tetramethylammonium perrhenate(VII), [N₁₁₁₁][ReO₄], and hexamethylrhenium(VI), Re(CH₃)₆, were used to extend our previously developed all-atom force field for organometallic compounds, to rhenium species. The new parametrization was able to reproduce the enthalpies of sublimation and unit cell parameters of the test set with maximum absolute deviations of 3.3 kJmol-1 and < 3.8%, respectively. The transferability of the interaction (ε) and atomic diameter (σ) parameters of the Lennard-Jones (12-6) potential function, previously observed for first and second-row transition metals, was also found to be valid for rhenium and tungsten (third-row metals).

 

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