A Benchmark Ab Initio and DFT Study of the Structure and Binding of Methane in the σ-Alkane Complex CpRe(CO)2(CH4).

Ab initio molecular orbital theory and density functional theory (DFT) procedures have been used to study the binding of methane in CpRe(CO)2(CH4), the simplest σ-alkane complex in the experimentally widely studied CpRe(CO)2(alkane) family. We find the optimal Re···C, Re···H and C···H distances to be 2.60, 1.92, and 1.15 Å, respectively, on the composite-CCSD(T)/def2-QZVPP (CCSD(T)/def2-TZVP with supplement for the larger def2-QZVPP basis set at the second-order Møller-Plesset perturbation theory level) potential energy surface which has been mapped out at this level of theory. The enthalpy of binding at 298 K was determined to be 62.0 kJ mol(-1) at the composite-CCSD(T)/CBS//B3-PW91/aug-cc-pVTZ-PP level. Benchmarks on the various DFT procedures show that some functionals give good geometries but underestimate binding energies, while others yield poor geometries but give closer agreements with the composite-CCSD(T) binding energy. On the other hand, the ωB97X-D functional gives fair agreements with composite-CCSD(T) for both geometry optimization as well as binding energy. Thus, it appears to be a reliable, easily implemented, and cost-effective means for studying Re-alkane complexes. Good binding energies are also obtained with several common functionals when D3 dispersion corrections are applied. Selected dispersion-corrected DFT methods (B3PW91-D3, TPSSh-D3, and B98-D3) were found to be quite accurate for the calculation of binding energies of several other model metal-CH4 complexes containing a range of metal centers (Rh, Pd, W, Ir, Pt). We also note that, for single-point energy calculation of the Re-CH4 binding, the PWP-B95-D3 double-hybrid DFT procedure provides an excellent agreement with the benchmark energy at only a slightly higher computational requirement.