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

Highlights: • The enthalpies of sublimation of CH₃ReO₃ and Re₂(CO)₁₀ were measured by Calvet microcalorimetry. • The molecular and crystal structure of CH₃ReO₃ was determined by X-ray diffraction. • An all-atom force field (FF) for organometallic compounds was extended to rhenium species. • MD simulations using that FF predicted ${\Delta }_{\text{sub}}{H}_{\text{m}}^{\text{o}}$ and unit cell parameters with a maximum deviation of ∼3%. -- Abstract: The standard (p° = 0.1 MPa) molar enthalpies of sublimation, at 298.15 K, of methyltrioxorhenium(VII), ${\Delta }_{\text{sub}}{H}_{\text{m}}^{\text{o}}$[CH₃ReO₃] = 70.2 ± 0.4 kJ mol⁻¹, and dirhenium decacarbonyl, ${\Delta }_{\text{sub}}{H}_{\text{m}}^{\text{o}}$[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 information 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 kJ^⋅mol⁻¹ and <3.8%, respectively. The transferability of the interaction (ε) and atomic diameter (σ) parameters of the Lennard-Jones (12–6) potential function, observed for first and second-row transition metals, was also found to be valid for rhenium and tungsten (third-row metals).