TY  - JOUR
AU  - Hansen, Andreas
AU  - Bannwarth, Christoph
AU  - Grimme, Stefan
AU  - Petrovic, Predrag V.
AU  - Werle, Christophe
AU  - Djukic, Jean-Pierre
PY  - 2014
UR  - http://cherry.chem.bg.ac.rs/handle/123456789/5371
AB  - Reliable thermochemical measurements and theoretical predictions for reactions involving large transition metal complexes
in which long-range intramolecular London dispersion interactions contribute significantly to their stabilization are still a challenge, particularly for reactions in solution. As an illustrative
and chemically important example, two reactions are investigated where a large dipalladium complex is quenched by
bulky phosphane ligands (triphenylphosphane and tricyclohexylphosphane). Reaction enthalpies and Gibbs free energies
were measured by isotherm titration calorimetry (ITC) and theoretically ‘back-corrected’ to yield 0 K gas-phase reaction energies (DE). It is shown that the Gibbs free solvation energy calculated with continuum models represents the largest source
of error in theoretical thermochemistry protocols. The (‘backcorrected’) experimental reaction energies were used to
benchmark (dispersion-corrected) density functional and wave
function theory methods. Particularly, we investigated whether
the atom-pairwise D3 dispersion correction is also accurate for
transition metal chemistry, and how accurately recently developed local coupled-cluster methods describe the important
long-range electron correlation contributions. Both, modern
dispersion-corrected density functions (e.g., PW6B95-D3(BJ) or
B3LYP-NL), as well as the now possible DLPNO-CCSD(T) calculations, are within the ‘experimental’ gas phase reference value.
The remaining uncertainties of 2–3 kcalmol1 can be essentially attributed to the solvation models. Hence, the future for accurate theoretical thermochemistry of large transition metal reactions in solution is very promising
PB  - Wiley-VCH Verlag GmbH & Co. KGaA
T2  - ChemistryOpen
T1  - The Thermochemistry of London Dispersion-Driven Transition Metal Reactions: Getting the ‘Right Answer for the Right Reason’
VL  - 3
SP  - 177
EP  - 189
DO  - 10.1002/open.201402017
ER  - 

@article{
author = "Hansen, Andreas and Bannwarth, Christoph and Grimme, Stefan and Petrovic, Predrag V. and Werle, Christophe and Djukic, Jean-Pierre",
year = "2014",
abstract = "Reliable thermochemical measurements and theoretical predictions for reactions involving large transition metal complexes
in which long-range intramolecular London dispersion interactions contribute significantly to their stabilization are still a challenge, particularly for reactions in solution. As an illustrative
and chemically important example, two reactions are investigated where a large dipalladium complex is quenched by
bulky phosphane ligands (triphenylphosphane and tricyclohexylphosphane). Reaction enthalpies and Gibbs free energies
were measured by isotherm titration calorimetry (ITC) and theoretically ‘back-corrected’ to yield 0 K gas-phase reaction energies (DE). It is shown that the Gibbs free solvation energy calculated with continuum models represents the largest source
of error in theoretical thermochemistry protocols. The (‘backcorrected’) experimental reaction energies were used to
benchmark (dispersion-corrected) density functional and wave
function theory methods. Particularly, we investigated whether
the atom-pairwise D3 dispersion correction is also accurate for
transition metal chemistry, and how accurately recently developed local coupled-cluster methods describe the important
long-range electron correlation contributions. Both, modern
dispersion-corrected density functions (e.g., PW6B95-D3(BJ) or
B3LYP-NL), as well as the now possible DLPNO-CCSD(T) calculations, are within the ‘experimental’ gas phase reference value.
The remaining uncertainties of 2–3 kcalmol1 can be essentially attributed to the solvation models. Hence, the future for accurate theoretical thermochemistry of large transition metal reactions in solution is very promising",
publisher = "Wiley-VCH Verlag GmbH & Co. KGaA",
journal = "ChemistryOpen",
title = "The Thermochemistry of London Dispersion-Driven Transition Metal Reactions: Getting the ‘Right Answer for the Right Reason’",
volume = "3",
pages = "177-189",
doi = "10.1002/open.201402017"
}

Hansen, A., Bannwarth, C., Grimme, S., Petrovic, P. V., Werle, C.,& Djukic, J.. (2014). The Thermochemistry of London Dispersion-Driven Transition Metal Reactions: Getting the ‘Right Answer for the Right Reason’. in ChemistryOpen
Wiley-VCH Verlag GmbH & Co. KGaA., 3, 177-189.
https://doi.org/10.1002/open.201402017

Hansen A, Bannwarth C, Grimme S, Petrovic PV, Werle C, Djukic J. The Thermochemistry of London Dispersion-Driven Transition Metal Reactions: Getting the ‘Right Answer for the Right Reason’. in ChemistryOpen. 2014;3:177-189.
doi:10.1002/open.201402017 .

Hansen, Andreas, Bannwarth, Christoph, Grimme, Stefan, Petrovic, Predrag V., Werle, Christophe, Djukic, Jean-Pierre, "The Thermochemistry of London Dispersion-Driven Transition Metal Reactions: Getting the ‘Right Answer for the Right Reason’" in ChemistryOpen, 3 (2014):177-189,
https://doi.org/10.1002/open.201402017 . .