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.
Highlights
Synthetic methods allowing one-step C−C bond formation through a metal-mediated transformation of C−H bonds have become increasingly important in both industry and basic research.[1−6] Potential routes for selective C−H bond activation and subsequent C−C bond formation in alkenes and aromatic compounds include the hydroarylation of unsaturated compounds by the addition of aromatic C−H bonds across an unsaturated C C bond or their oxidative coupling that preserves the double bond
The results presented in this work demonstrate that the DLPNO-CCSD(T1) approximation with TightPNO cutoffs closely reproduces the canonical CCSD(T) results for Ru(II) complexes, with the largest MAD (2.18 kcal/mol) found for ligand coordination reactions
For open-shell Ru(III) complexes, the DLPNO-CCSD(T1) TightPNO approach fortuitously showed better performance for ligand coordination (LC) than its closed-shell equivalent (MAD = 1.34 kcal/mol) and closely reproduced other types of energetics, with the largest MAD of 2.06 kcal/mol found for the energies of intermediates
Summary
Synthetic methods allowing one-step C−C bond formation through a metal-mediated transformation of C−H bonds have become increasingly important in both industry and basic research.[1−6] Potential routes for selective C−H bond activation and subsequent C−C bond formation in alkenes and aromatic compounds include the hydroarylation of unsaturated compounds by the addition of aromatic C−H bonds across an unsaturated C C bond or their oxidative coupling that preserves the double bond. Motivated by the experimental results of Milstein and coworkers,[8] over a decade ago we first attempted to explore the mechanism of the oxidative coupling of arenes with alkenes in the presence of [(η6-C6H6)RuCl2]2 or RuCl3·3H2O in a CO atmosphere as well as to compare it with the mechanism of the concurrent reaction of the hydroarylation of olefins (Scheme 1). In this preliminary work (reported in part in a conference proceedings extended abstract10), we employed hybrid and double-hybrid DFT. We have reexamined the mechanisms of Rucatalyzed hydroarylation and oxidative coupling using wave
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