Coupled Cluster Benchmark of New DFT and Local Correlation Methods: Mechanisms of Hydroarylation and Oxidative Coupling Catalyzed by Ru(II, III) Chloride Carbonyls

Abstract

We have evaluated a set of accurate canonical CCSD­(T) energies for stationary points on the potential energy surface for Ru­(II, III) chloride carbonyl catalysis of two competing reactions between benzene and methyl acrylate (MA), namely, hydroarylation and oxidative coupling. We have then applied this set to evaluate the performance of localized orbital coupled-cluster methods and several new and common density functionals. We find that (a) DLPNO-CCSD­(T) with TightPNO cutoffs is an acceptable substitute for full canonical CCSD­(T) calculations on this system; (b) for the closed-shell systems where it could be applied, LNO-CCSD­(T) with tight convergence criteria is very close to the canonical results; (c) the recent ωB97X-V and ωB97M-V functionals exhibit superior performance to commonly used DFT functionals in both closed- and open-shell calculations; (d) the revDSD-PBEP86 revision of the DSD-PBEP86 double hybrid represents an improvement over the original, even though transition metals were not involved in its parametrization; and (e) DSD-SCAN and DOD-SCAN show comparable efficiency. Most tested (meta)-GGA and hybrid density functionals perform better for open-shell than for closed-shell complexes; this is not the case for the double hybrids considered.

The role of the intermediate triplet state in iron-catalyzed multi-state C–H activation

“…In addition to the B3LYP functional that has been shown to reproduce spin-dependent properties of iron complexes, [50][51][52][53] oB97X-V functionals, which are known to work well for transition metal compounds. 33,54,55 All three density functionals predict the same order of the spin states for the reactant geometries (E quintet o E triplet o E singlet ) and the TS geometries (E singlet o E quintet o E triplet ), with the exception of the isoenergetic singlet and triplet states at the reactant geometry predicted by oB97X-V and the different state order at the TS geometries predicted by MN15-L (Table 1). For the TS geometries, this order of the spin states is also consistent with the CCSD(T) results.…”

“…In addition to the B3LYP functional that has been shown to reproduce spin-dependent properties of iron complexes, 50–53 we tested the MN15-L and ωB97X-V functionals, which are known to work well for transition metal compounds. 33,54,55…”

The MOBH35 Metal–Organic Barrier Heights Reconsidered: Performance of Local-Orbital Coupled Cluster Approaches in Different Static Correlation Regimes

“…As the present paper was finalized for publication, a reviewer of ref raised an issue that might potentially have some bearing on the present work.…”

Do Double-Hybrid Functionals Benefit from Regularization in the PT2 Term? Observations from an Extensive Benchmark

“…As such, DHDF theory resides on the seamline between density functional theory (DFT) and wave function approaches. DHDFs are the most accurate DFT methods available to date for main group energetics, − transition metal catalysis, − electronic excitation spectroscopy, − external magnetic − and electric field , induced properties, and vibrational frequencies . Its reliance on a second-order perturbation theory term for part of the correlation energy creates an Achilles’ heel for molecules with small band gaps, due to the presence of orbital energy differences in the denominator.…”