TY  - JOUR
AU  - Milovanović, Milan R.
AU  - Boucher, Mélanie
AU  - Cornaton, Yann
AU  - Zarić, Snežana D.
AU  - Pfeffer, Michel
AU  - Djukic, Jean-Pierre
PY  - 2021
UR  - https://onlinelibrary.wiley.com/doi/abs/10.1002/ejic.202100750
UR  - C:\Users\Ana\Zotero\storage\ZAYTN3C5\Milovanović et al. - 2021 - The Thermochemistry of Alkyne Insertion into a Pal.pdf
UR  - C:\Users\Ana\Zotero\storage\JYEI976E\ejic.html
UR  - http://cherry.chem.bg.ac.rs/handle/123456789/4783
AB  - In an effort to determine the thermochemistry of established organometallic transformation, the well documented reaction of alkynes with a palladacycle was investigated by isothermal titration calorimetry (ITC). Although the mechanism of the insertion of unsaturated substrates into the Pd−C bond of cyclopalladated compounds is known, no information is available so far about their thermochemistry. The enthalpies of the reactions of Ph−C≡C−Ph and MeOC(O)−C≡C(O)COMe with the bisacetonitrilo salt of the N,N-benzylamine palladacycle were determined by ITC in chlorobenzene after having optimized the conditions to ensure that only the double and a single insertion of alkynes were occurring respectively. The reaction energy profile established by DFT for the double insertion process involving Ph−C≡C−Ph confirmed earlier conclusions on the rate determining character of the first insertion. Further computations of reaction enthalpies reveal significant discrepancies between ITC and DFT-D/continuum solvation enthalpies, that are suspected to arise from an unexpected explicit noncovalent interaction of PhCl with the components of the reaction.
PB  - Wiley
T2  - European Journal of Inorganic Chemistry
T1  - The Thermochemistry of Alkyne Insertion into a Palladacycle Outlines the Solvation Conundrum in DFT
VL  - 2021
IS  - 45
SP  - 4690
EP  - 4699
DO  - 10.1002/ejic.202100750
ER  - 

@article{
author = "Milovanović, Milan R. and Boucher, Mélanie and Cornaton, Yann and Zarić, Snežana D. and Pfeffer, Michel and Djukic, Jean-Pierre",
year = "2021",
abstract = "In an effort to determine the thermochemistry of established organometallic transformation, the well documented reaction of alkynes with a palladacycle was investigated by isothermal titration calorimetry (ITC). Although the mechanism of the insertion of unsaturated substrates into the Pd−C bond of cyclopalladated compounds is known, no information is available so far about their thermochemistry. The enthalpies of the reactions of Ph−C≡C−Ph and MeOC(O)−C≡C(O)COMe with the bisacetonitrilo salt of the N,N-benzylamine palladacycle were determined by ITC in chlorobenzene after having optimized the conditions to ensure that only the double and a single insertion of alkynes were occurring respectively. The reaction energy profile established by DFT for the double insertion process involving Ph−C≡C−Ph confirmed earlier conclusions on the rate determining character of the first insertion. Further computations of reaction enthalpies reveal significant discrepancies between ITC and DFT-D/continuum solvation enthalpies, that are suspected to arise from an unexpected explicit noncovalent interaction of PhCl with the components of the reaction.",
publisher = "Wiley",
journal = "European Journal of Inorganic Chemistry",
title = "The Thermochemistry of Alkyne Insertion into a Palladacycle Outlines the Solvation Conundrum in DFT",
volume = "2021",
number = "45",
pages = "4690-4699",
doi = "10.1002/ejic.202100750"
}

Milovanović, M. R., Boucher, M., Cornaton, Y., Zarić, S. D., Pfeffer, M.,& Djukic, J.. (2021). The Thermochemistry of Alkyne Insertion into a Palladacycle Outlines the Solvation Conundrum in DFT. in European Journal of Inorganic Chemistry
Wiley., 2021(45), 4690-4699.
https://doi.org/10.1002/ejic.202100750

Milovanović MR, Boucher M, Cornaton Y, Zarić SD, Pfeffer M, Djukic J. The Thermochemistry of Alkyne Insertion into a Palladacycle Outlines the Solvation Conundrum in DFT. in European Journal of Inorganic Chemistry. 2021;2021(45):4690-4699.
doi:10.1002/ejic.202100750 .

Milovanović, Milan R., Boucher, Mélanie, Cornaton, Yann, Zarić, Snežana D., Pfeffer, Michel, Djukic, Jean-Pierre, "The Thermochemistry of Alkyne Insertion into a Palladacycle Outlines the Solvation Conundrum in DFT" in European Journal of Inorganic Chemistry, 2021, no. 45 (2021):4690-4699,
https://doi.org/10.1002/ejic.202100750 . .

TY  - CONF
AU  - Milovanović, Milan R.
AU  - Dherbassy, Quentin
AU  - Wencel-Delord, Joanna
AU  - Colobert, Françoise
AU  - Zarić, Snežana D.
AU  - Djukic, Jean-Pierre
PY  - 2020
UR  - http://cherry.chem.bg.ac.rs/handle/123456789/6357
AB  - HFIP, i.e. 1,1,1,3,3,3-hexafluoropropan-2-ol, was found to be an exceptional medium,[1] either as solvent or co-solvent, that allows many reactions to occur.[2-5] However, the exact role and mode of action of HFIP in various chemical transformations still remains elusive. Despite many reports dealing with water/HFIP complexes, little has been published on other molecular complexes of HFIP as well as on thermochemistry of the formation of such complexes.[6]
Within this study the affinity of a series of eight different Lewis bases (3 sulfoxides, 3 Nsp2 pyridine derivatives, 1 aromatic amine, 1 cyclic aliphatic ether) to HFIP (as Lewis acid) is investigated 
experimentally by Isothermal Titration Calorimetry (ITC) and theoretically using static DFT-D calculations. Measured ITC association enthalpy values ΔHaITC spanned -9.3 kcal/mol - -14
kcal/mol. Computations including a PCM implicit solvation model produced similar exothermicity of association of all studied systems - ΔHa values ranging -8.5 – -12.7 kcal/mol. In general, most of interaction energy is due to the hydrogen bonding and not due to formation of significantly strong halogen bonds. An additional set of calculations combining implicit and explicit solvation by chlorobenzene of the reactants, pointed out the relatively low interference of the solvent with the HFIPbase complexation, which main effect is to slightly enhance the Gibbs energy of the HFIP-Lewis base association. It is speculated that the interactions of bulk HFIP with Lewis bases therefore may significantly intervene in catalytic processes not only via the dynamic miscrostructuration of the medium but also more explicitly by affecting bonds’ polarization at the Lewis bases.
C3  - The 4th International Symposium on Halogen Bonding (ISXB4), Stellenbosch University, South Africa, 2-5 November 2020
T1  - Joint ITC and DFT Study of the Affinity of Some Lewis Bases to HIFP in Solution
SP  - 161
EP  - 161
UR  - https://hdl.handle.net/21.15107/rcub_cherry_6357
ER  - 

@conference{
author = "Milovanović, Milan R. and Dherbassy, Quentin and Wencel-Delord, Joanna and Colobert, Françoise and Zarić, Snežana D. and Djukic, Jean-Pierre",
year = "2020",
abstract = "HFIP, i.e. 1,1,1,3,3,3-hexafluoropropan-2-ol, was found to be an exceptional medium,[1] either as solvent or co-solvent, that allows many reactions to occur.[2-5] However, the exact role and mode of action of HFIP in various chemical transformations still remains elusive. Despite many reports dealing with water/HFIP complexes, little has been published on other molecular complexes of HFIP as well as on thermochemistry of the formation of such complexes.[6]
Within this study the affinity of a series of eight different Lewis bases (3 sulfoxides, 3 Nsp2 pyridine derivatives, 1 aromatic amine, 1 cyclic aliphatic ether) to HFIP (as Lewis acid) is investigated 
experimentally by Isothermal Titration Calorimetry (ITC) and theoretically using static DFT-D calculations. Measured ITC association enthalpy values ΔHaITC spanned -9.3 kcal/mol - -14
kcal/mol. Computations including a PCM implicit solvation model produced similar exothermicity of association of all studied systems - ΔHa values ranging -8.5 – -12.7 kcal/mol. In general, most of interaction energy is due to the hydrogen bonding and not due to formation of significantly strong halogen bonds. An additional set of calculations combining implicit and explicit solvation by chlorobenzene of the reactants, pointed out the relatively low interference of the solvent with the HFIPbase complexation, which main effect is to slightly enhance the Gibbs energy of the HFIP-Lewis base association. It is speculated that the interactions of bulk HFIP with Lewis bases therefore may significantly intervene in catalytic processes not only via the dynamic miscrostructuration of the medium but also more explicitly by affecting bonds’ polarization at the Lewis bases.",
journal = "The 4th International Symposium on Halogen Bonding (ISXB4), Stellenbosch University, South Africa, 2-5 November 2020",
title = "Joint ITC and DFT Study of the Affinity of Some Lewis Bases to HIFP in Solution",
pages = "161-161",
url = "https://hdl.handle.net/21.15107/rcub_cherry_6357"
}

Milovanović, M. R., Dherbassy, Q., Wencel-Delord, J., Colobert, F., Zarić, S. D.,& Djukic, J.. (2020). Joint ITC and DFT Study of the Affinity of Some Lewis Bases to HIFP in Solution. in The 4th International Symposium on Halogen Bonding (ISXB4), Stellenbosch University, South Africa, 2-5 November 2020, 161-161.
https://hdl.handle.net/21.15107/rcub_cherry_6357

Milovanović MR, Dherbassy Q, Wencel-Delord J, Colobert F, Zarić SD, Djukic J. Joint ITC and DFT Study of the Affinity of Some Lewis Bases to HIFP in Solution. in The 4th International Symposium on Halogen Bonding (ISXB4), Stellenbosch University, South Africa, 2-5 November 2020. 2020;:161-161.
https://hdl.handle.net/21.15107/rcub_cherry_6357 .

Milovanović, Milan R., Dherbassy, Quentin, Wencel-Delord, Joanna, Colobert, Françoise, Zarić, Snežana D., Djukic, Jean-Pierre, "Joint ITC and DFT Study of the Affinity of Some Lewis Bases to HIFP in Solution" in The 4th International Symposium on Halogen Bonding (ISXB4), Stellenbosch University, South Africa, 2-5 November 2020 (2020):161-161,
https://hdl.handle.net/21.15107/rcub_cherry_6357 .

TY  - CONF
AU  - Milovanović, Milan R.
AU  - Andrić, Jelena M.
AU  - Medaković, Vesna
AU  - Djukic, Jean-Pierre
AU  - Zarić, Snežana D.
PY  - 2019
UR  - http://cherry.chem.bg.ac.rs/handle/123456789/6361
AB  - The phosphine–borane pairs, especially frustrated ones, have found great use in different domains: from synthesis and catalysis to hydrogen storage and materials [1]. Herein we studied the influence of the substituents on the phosphine–borane interactions based on the analysis of all available crystal structures archived in the Cambridge Structural Database (CSD) [2].
The contacts have been classified according to the size and the nature of the substituents on the boron atom, which enabled analysis of the influence of the different types of boron atom substituents on the geometry of phosphine–borane pairs, including classical and frustrated Lewis pairs (FLPs), in the crystal structures. Three sets of structures were considered: the BH3–P(Y1Y2Y3) set containing BH3 as the borane molecule; the B(X1X2X3)–P(Y1Y2Y3) set with all other borane molecules, and the frustrated Lewis (phosphine–borane) pairs set. The results show that the presence of aromatic substituents on the boron atom has a small influence, whereas the presence of a bridge (an atomic chain between phosphorus and boron centres) has a more significant influence on the geometries of phosphine–borane interactions in crystals. The obtained data also enabled a comparison of the geometrical parameters of the classical and frustrated Lewis pairs.
PB  - Belgrade : Serbian Crystallographic Society
C3  - 26th Conference of the Serbian Crystallographic Society, June 27–28rd, 2019 Silver lake, Serbia
T1  - The influence of the substituents on the interactions in phosphine–borane pairs
UR  - https://hdl.handle.net/21.15107/rcub_cherry_6361
ER  - 

@conference{
author = "Milovanović, Milan R. and Andrić, Jelena M. and Medaković, Vesna and Djukic, Jean-Pierre and Zarić, Snežana D.",
year = "2019",
abstract = "The phosphine–borane pairs, especially frustrated ones, have found great use in different domains: from synthesis and catalysis to hydrogen storage and materials [1]. Herein we studied the influence of the substituents on the phosphine–borane interactions based on the analysis of all available crystal structures archived in the Cambridge Structural Database (CSD) [2].
The contacts have been classified according to the size and the nature of the substituents on the boron atom, which enabled analysis of the influence of the different types of boron atom substituents on the geometry of phosphine–borane pairs, including classical and frustrated Lewis pairs (FLPs), in the crystal structures. Three sets of structures were considered: the BH3–P(Y1Y2Y3) set containing BH3 as the borane molecule; the B(X1X2X3)–P(Y1Y2Y3) set with all other borane molecules, and the frustrated Lewis (phosphine–borane) pairs set. The results show that the presence of aromatic substituents on the boron atom has a small influence, whereas the presence of a bridge (an atomic chain between phosphorus and boron centres) has a more significant influence on the geometries of phosphine–borane interactions in crystals. The obtained data also enabled a comparison of the geometrical parameters of the classical and frustrated Lewis pairs.",
publisher = "Belgrade : Serbian Crystallographic Society",
journal = "26th Conference of the Serbian Crystallographic Society, June 27–28rd, 2019 Silver lake, Serbia",
title = "The influence of the substituents on the interactions in phosphine–borane pairs",
url = "https://hdl.handle.net/21.15107/rcub_cherry_6361"
}

Milovanović, M. R., Andrić, J. M., Medaković, V., Djukic, J.,& Zarić, S. D.. (2019). The influence of the substituents on the interactions in phosphine–borane pairs. in 26th Conference of the Serbian Crystallographic Society, June 27–28rd, 2019 Silver lake, Serbia
Belgrade : Serbian Crystallographic Society..
https://hdl.handle.net/21.15107/rcub_cherry_6361

Milovanović MR, Andrić JM, Medaković V, Djukic J, Zarić SD. The influence of the substituents on the interactions in phosphine–borane pairs. in 26th Conference of the Serbian Crystallographic Society, June 27–28rd, 2019 Silver lake, Serbia. 2019;.
https://hdl.handle.net/21.15107/rcub_cherry_6361 .

Milovanović, Milan R., Andrić, Jelena M., Medaković, Vesna, Djukic, Jean-Pierre, Zarić, Snežana D., "The influence of the substituents on the interactions in phosphine–borane pairs" in 26th Conference of the Serbian Crystallographic Society, June 27–28rd, 2019 Silver lake, Serbia (2019),
https://hdl.handle.net/21.15107/rcub_cherry_6361 .

TY  - CONF
AU  - Milovanović, Milan R.
AU  - Djukic, Jean-Pierre
AU  - Zarić, Snežana D.
PY  - 2019
UR  - http://cherry.chem.bg.ac.rs/handle/123456789/6362
AB  - The understanding of certain, still unknown, aspects of the chemical bond is made possible by new theoretical tools, particularly static DFT-D or DFT methods corrected for dispersion. These methods allow accounting for, in a physically relevant way, the effects of dispersion at medium and long distance [1]. For the further assessing the accuracy of static DFT-D calculations the providing of referential experimental data was found to be essential. It has been shown that Isothermal titration calorimetry (ITC) techniques can provide reliable thermodynamic parameters of reaction (enthalpy ΔHr, Gibbs free energy ΔGr and entropy ΔSr) [2], while some recent studies showed good agreement between experimental and theoretical results [2].
The study presented here sheds some light on the thermochemistry of reactions in solution by preforming ITC experiments in chlorobenzene and static DFT-D calculations. The study points out that, in cases where solvent molecules can interact significantly with molecules of reactants, an accounting for the explicit solvation is of crucial importance for agreement between experiment and theory. The results of various kinds of organometallic reactions will be presented in some details.
PB  - Belgrade : Serbian Chemical Society
C3  - 7th Conference of the Young Chemists of Serbia, Book of Abstracts, Belgrade, 2nd November 2019
T1  - Thermochemistry of organometallic reactions in solution: joint ITC and DFT study
UR  - https://hdl.handle.net/21.15107/rcub_cherry_6362
ER  - 

@conference{
author = "Milovanović, Milan R. and Djukic, Jean-Pierre and Zarić, Snežana D.",
year = "2019",
abstract = "The understanding of certain, still unknown, aspects of the chemical bond is made possible by new theoretical tools, particularly static DFT-D or DFT methods corrected for dispersion. These methods allow accounting for, in a physically relevant way, the effects of dispersion at medium and long distance [1]. For the further assessing the accuracy of static DFT-D calculations the providing of referential experimental data was found to be essential. It has been shown that Isothermal titration calorimetry (ITC) techniques can provide reliable thermodynamic parameters of reaction (enthalpy ΔHr, Gibbs free energy ΔGr and entropy ΔSr) [2], while some recent studies showed good agreement between experimental and theoretical results [2].
The study presented here sheds some light on the thermochemistry of reactions in solution by preforming ITC experiments in chlorobenzene and static DFT-D calculations. The study points out that, in cases where solvent molecules can interact significantly with molecules of reactants, an accounting for the explicit solvation is of crucial importance for agreement between experiment and theory. The results of various kinds of organometallic reactions will be presented in some details.",
publisher = "Belgrade : Serbian Chemical Society",
journal = "7th Conference of the Young Chemists of Serbia, Book of Abstracts, Belgrade, 2nd November 2019",
title = "Thermochemistry of organometallic reactions in solution: joint ITC and DFT study",
url = "https://hdl.handle.net/21.15107/rcub_cherry_6362"
}

Milovanović, M. R., Djukic, J.,& Zarić, S. D.. (2019). Thermochemistry of organometallic reactions in solution: joint ITC and DFT study. in 7th Conference of the Young Chemists of Serbia, Book of Abstracts, Belgrade, 2nd November 2019
Belgrade : Serbian Chemical Society..
https://hdl.handle.net/21.15107/rcub_cherry_6362

Milovanović MR, Djukic J, Zarić SD. Thermochemistry of organometallic reactions in solution: joint ITC and DFT study. in 7th Conference of the Young Chemists of Serbia, Book of Abstracts, Belgrade, 2nd November 2019. 2019;.
https://hdl.handle.net/21.15107/rcub_cherry_6362 .

Milovanović, Milan R., Djukic, Jean-Pierre, Zarić, Snežana D., "Thermochemistry of organometallic reactions in solution: joint ITC and DFT study" in 7th Conference of the Young Chemists of Serbia, Book of Abstracts, Belgrade, 2nd November 2019 (2019),
https://hdl.handle.net/21.15107/rcub_cherry_6362 .

TY  - JOUR
AU  - Milovanović, Milan R.
AU  - Dohm, Sebastian
AU  - Hansen, Andreas
AU  - Djukic, Jean-Pierre
AU  - Zarić, Snežana D.
AU  - Grimme, Stefan
PY  - 2017
UR  - https://akcongress.com/jtacc
UR  - http://cherry.chem.bg.ac.rs/handle/123456789/6364
AB  - The London forces [1–3], or dispersion, are omnipresent in the nature. It constitutes an important part of the energy contribution to the stabilization of the tertiary structure of peptides, other natural polymers and the spontaneous coalescence of atomic aggregates or apolar molecules. The specifi city of the force of London is that it acts at long distances and it is always attractive, and it is therefore effective intramolecularly and determines in many situations the conformational behaviour of organic molecules and organometallics as well. It plays an essential role in chiral recognition and discrimination processes.
The understanding of certain still unknown aspects of the chemical bond is made possible by new theoretical tools, particularly static DFT-D or DFT methods corrected for Dispersion. These allow to account for in a physically relevant way the effects of dispersion at medium and long distance [4]. For the further assessing the accuracy of static DFT-D calculations providing a referential of experimental data was found essential.
It has been shown that ITC techniques can provide reliable reaction enthalpy ΔHr, Gibbs free energy of reaction ΔGr and reaction entropy ΔSr as well [5]. Some recent studies showed good agreement between experimental and theoretical results [6–8]. This study will shed some light on the thermochemistry of the reactions in solution by preforming ITC experiments in chlorobenzene, from one side, and static DFT-D calculations at different levels of theory, from another side (Fig. 1). By comparison of obtained results one could conclude on the
excellent agreement between experimental and theoretical data, which could be promising for the further development and application of static DFT-D computational methods. As examples, the results of various organometallic reactions will be presented in some details [9].
T2  - 1st Journal of Thermal Analysis and Caliometry Conference and 6th V4 (Joint Chech-Hungarian-Polish-Slovakian) Thermoanalytical Conference, Book of Abstracts, June 6-9, 2017, Budapest, Hungary
T1  - Benchmarking to DFT-d calculations by ITC experimental data
UR  - https://hdl.handle.net/21.15107/rcub_cherry_6364
ER  - 

@article{
author = "Milovanović, Milan R. and Dohm, Sebastian and Hansen, Andreas and Djukic, Jean-Pierre and Zarić, Snežana D. and Grimme, Stefan",
year = "2017",
abstract = "The London forces [1–3], or dispersion, are omnipresent in the nature. It constitutes an important part of the energy contribution to the stabilization of the tertiary structure of peptides, other natural polymers and the spontaneous coalescence of atomic aggregates or apolar molecules. The specifi city of the force of London is that it acts at long distances and it is always attractive, and it is therefore effective intramolecularly and determines in many situations the conformational behaviour of organic molecules and organometallics as well. It plays an essential role in chiral recognition and discrimination processes.
The understanding of certain still unknown aspects of the chemical bond is made possible by new theoretical tools, particularly static DFT-D or DFT methods corrected for Dispersion. These allow to account for in a physically relevant way the effects of dispersion at medium and long distance [4]. For the further assessing the accuracy of static DFT-D calculations providing a referential of experimental data was found essential.
It has been shown that ITC techniques can provide reliable reaction enthalpy ΔHr, Gibbs free energy of reaction ΔGr and reaction entropy ΔSr as well [5]. Some recent studies showed good agreement between experimental and theoretical results [6–8]. This study will shed some light on the thermochemistry of the reactions in solution by preforming ITC experiments in chlorobenzene, from one side, and static DFT-D calculations at different levels of theory, from another side (Fig. 1). By comparison of obtained results one could conclude on the
excellent agreement between experimental and theoretical data, which could be promising for the further development and application of static DFT-D computational methods. As examples, the results of various organometallic reactions will be presented in some details [9].",
journal = "1st Journal of Thermal Analysis and Caliometry Conference and 6th V4 (Joint Chech-Hungarian-Polish-Slovakian) Thermoanalytical Conference, Book of Abstracts, June 6-9, 2017, Budapest, Hungary",
title = "Benchmarking to DFT-d calculations by ITC experimental data",
url = "https://hdl.handle.net/21.15107/rcub_cherry_6364"
}

Milovanović, M. R., Dohm, S., Hansen, A., Djukic, J., Zarić, S. D.,& Grimme, S.. (2017). Benchmarking to DFT-d calculations by ITC experimental data. in 1st Journal of Thermal Analysis and Caliometry Conference and 6th V4 (Joint Chech-Hungarian-Polish-Slovakian) Thermoanalytical Conference, Book of Abstracts, June 6-9, 2017, Budapest, Hungary.
https://hdl.handle.net/21.15107/rcub_cherry_6364

Milovanović MR, Dohm S, Hansen A, Djukic J, Zarić SD, Grimme S. Benchmarking to DFT-d calculations by ITC experimental data. in 1st Journal of Thermal Analysis and Caliometry Conference and 6th V4 (Joint Chech-Hungarian-Polish-Slovakian) Thermoanalytical Conference, Book of Abstracts, June 6-9, 2017, Budapest, Hungary. 2017;.
https://hdl.handle.net/21.15107/rcub_cherry_6364 .

Milovanović, Milan R., Dohm, Sebastian, Hansen, Andreas, Djukic, Jean-Pierre, Zarić, Snežana D., Grimme, Stefan, "Benchmarking to DFT-d calculations by ITC experimental data" in 1st Journal of Thermal Analysis and Caliometry Conference and 6th V4 (Joint Chech-Hungarian-Polish-Slovakian) Thermoanalytical Conference, Book of Abstracts, June 6-9, 2017, Budapest, Hungary (2017),
https://hdl.handle.net/21.15107/rcub_cherry_6364 .

TY  - CHAP
AU  - Petrović, Predrag
AU  - Djukic, Jean Pierre
AU  - Hansen, Andreas
AU  - Bannwarth, Christoph
AU  - Grimme, Stefan
PY  - 2016
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/299
AB  - Non-covalent interactions (NCIs) are ubiquitous in nature, and the demonstration of their role in transition metal chemistry remains a vivid domain of research. Indeed, a better understanding of the interplay of NCIs with covalent interactions remains critical as it may create the basis for new conceptual frameworks for the engineering of new functional organometallic complexes. This chapter deals with the challenges of the research in ab initio quantum chemistry particularly in its contribution to the modeling of organometallic systems with their inherent complexity. Including the contribution of NCIs into the analysis of chemical bonds and other bonding relationships is at reach with recently developed methods. Views and analyses of novel methodologies developed to produce a more accurate evaluation of the thermochemistry of reactions involving transition metal complexes in solution are presented. The intramolecular stabilizing role of NCIs is also reviewed for particular cases of bimetallic d-block transition metal complexes that challenge, by their structural features, the empirical Langmuir-Sidgwick 18 electron rule. The treatment of the literature corpus of data is presented in a chronological fashion to outline the changes of practice over the years in the treatment of metal-metal interactions from a deductionist approach based on structural informations produced by static crystal X-ray diffraction analyses toward a comprehensive apprehension of bonding taking into consideration inherent molecular dynamics. Further review of intermolecular stabilizing effects of NCIs in peculiar cases of transition metal-based donor-acceptor complexes and other aggregates of transition metal complexes that display remarkable persistence in solution is presented. © 2016 John Wiley & Sons, Inc.
T2  - Non-covalent Interactions in the Synthesis and Design of New Compounds
T1  - Non-covalent Stabilization in Transition Metal Coordination and Organometallic Complexes
SP  - 115
EP  - 143
DO  - 10.1002/9781119113874.ch7
ER  - 

@inbook{
author = "Petrović, Predrag and Djukic, Jean Pierre and Hansen, Andreas and Bannwarth, Christoph and Grimme, Stefan",
year = "2016",
abstract = "Non-covalent interactions (NCIs) are ubiquitous in nature, and the demonstration of their role in transition metal chemistry remains a vivid domain of research. Indeed, a better understanding of the interplay of NCIs with covalent interactions remains critical as it may create the basis for new conceptual frameworks for the engineering of new functional organometallic complexes. This chapter deals with the challenges of the research in ab initio quantum chemistry particularly in its contribution to the modeling of organometallic systems with their inherent complexity. Including the contribution of NCIs into the analysis of chemical bonds and other bonding relationships is at reach with recently developed methods. Views and analyses of novel methodologies developed to produce a more accurate evaluation of the thermochemistry of reactions involving transition metal complexes in solution are presented. The intramolecular stabilizing role of NCIs is also reviewed for particular cases of bimetallic d-block transition metal complexes that challenge, by their structural features, the empirical Langmuir-Sidgwick 18 electron rule. The treatment of the literature corpus of data is presented in a chronological fashion to outline the changes of practice over the years in the treatment of metal-metal interactions from a deductionist approach based on structural informations produced by static crystal X-ray diffraction analyses toward a comprehensive apprehension of bonding taking into consideration inherent molecular dynamics. Further review of intermolecular stabilizing effects of NCIs in peculiar cases of transition metal-based donor-acceptor complexes and other aggregates of transition metal complexes that display remarkable persistence in solution is presented. © 2016 John Wiley & Sons, Inc.",
journal = "Non-covalent Interactions in the Synthesis and Design of New Compounds",
booktitle = "Non-covalent Stabilization in Transition Metal Coordination and Organometallic Complexes",
pages = "115-143",
doi = "10.1002/9781119113874.ch7"
}

Petrović, P., Djukic, J. P., Hansen, A., Bannwarth, C.,& Grimme, S.. (2016). Non-covalent Stabilization in Transition Metal Coordination and Organometallic Complexes. in Non-covalent Interactions in the Synthesis and Design of New Compounds, 115-143.
https://doi.org/10.1002/9781119113874.ch7

Petrović P, Djukic JP, Hansen A, Bannwarth C, Grimme S. Non-covalent Stabilization in Transition Metal Coordination and Organometallic Complexes. in Non-covalent Interactions in the Synthesis and Design of New Compounds. 2016;:115-143.
doi:10.1002/9781119113874.ch7 .

Petrović, Predrag, Djukic, Jean Pierre, Hansen, Andreas, Bannwarth, Christoph, Grimme, Stefan, "Non-covalent Stabilization in Transition Metal Coordination and Organometallic Complexes" in Non-covalent Interactions in the Synthesis and Design of New Compounds (2016):115-143,
https://doi.org/10.1002/9781119113874.ch7 . .

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 . .

TY  - JOUR
AU  - Iali, Wissam
AU  - Petrovic, Predrag V.
AU  - Pfeffer, Michel
AU  - Grimme, Stefan
AU  - Djukic, Jean-Pierre
PY  - 2012
UR  - http://cherry.chem.bg.ac.rs/handle/123456789/5372
AB  - A series of iridacycles bearing π-bonded moieties of variable electron-withdrawing capabilities were tested for their ability to promote water oxidation catalysis (WOC) in the presence of high loading in a sacrificial oxidant, under conditions chosen for optimal dioxygen production. This report shows that none of these complexes performs differently than monometallic iridacycles and that the π-bonded moiety does not affect the overall rate of O2 production. Furthermore, it is shown that cucurbituril macrocycles significantly inhibit the production of dioxygen independently of the nature of the Cp*Ir(III)-based catalyst used to perform WOC. Theoretical first-principles based DFT-D3 investigations including a complete treatment of solvation with COSMO and COSMO-RS treatments supported by ITC analyses suggest that concealment of the catalyst by curcurbit[7]uril could occur by non-covalent interaction of the Cp*Ir moiety in the hydrophobic pocket of the cavitand. For other cavitands of smaller inner cavity diameter, inclusion may not be the main mode of inhibition. Assuming the intervention of the putative Ir(IV)–oxyl biradical of a Cp*IrIV(O)(H2O)2 species like suggested by many authors, inhibition of WOC by inclusion would probably result from unfavourable coulombic interactions between water and the inclusion complex.
PB  - Royal Society of Chemistry
T2  - Dalton Transactions
T1  - The inhibition of iridium-promoted water oxidation catalysis (WOC) by cucurbit[n]urils
VL  - 41
SP  - 12233
DO  - 10.1039/C2DT31363D
ER  - 

@article{
author = "Iali, Wissam and Petrovic, Predrag V. and Pfeffer, Michel and Grimme, Stefan and Djukic, Jean-Pierre",
year = "2012",
abstract = "A series of iridacycles bearing π-bonded moieties of variable electron-withdrawing capabilities were tested for their ability to promote water oxidation catalysis (WOC) in the presence of high loading in a sacrificial oxidant, under conditions chosen for optimal dioxygen production. This report shows that none of these complexes performs differently than monometallic iridacycles and that the π-bonded moiety does not affect the overall rate of O2 production. Furthermore, it is shown that cucurbituril macrocycles significantly inhibit the production of dioxygen independently of the nature of the Cp*Ir(III)-based catalyst used to perform WOC. Theoretical first-principles based DFT-D3 investigations including a complete treatment of solvation with COSMO and COSMO-RS treatments supported by ITC analyses suggest that concealment of the catalyst by curcurbit[7]uril could occur by non-covalent interaction of the Cp*Ir moiety in the hydrophobic pocket of the cavitand. For other cavitands of smaller inner cavity diameter, inclusion may not be the main mode of inhibition. Assuming the intervention of the putative Ir(IV)–oxyl biradical of a Cp*IrIV(O)(H2O)2 species like suggested by many authors, inhibition of WOC by inclusion would probably result from unfavourable coulombic interactions between water and the inclusion complex.",
publisher = "Royal Society of Chemistry",
journal = "Dalton Transactions",
title = "The inhibition of iridium-promoted water oxidation catalysis (WOC) by cucurbit[n]urils",
volume = "41",
pages = "12233",
doi = "10.1039/C2DT31363D"
}

Iali, W., Petrovic, P. V., Pfeffer, M., Grimme, S.,& Djukic, J.. (2012). The inhibition of iridium-promoted water oxidation catalysis (WOC) by cucurbit[n]urils. in Dalton Transactions
Royal Society of Chemistry., 41, 12233.
https://doi.org/10.1039/C2DT31363D

Iali W, Petrovic PV, Pfeffer M, Grimme S, Djukic J. The inhibition of iridium-promoted water oxidation catalysis (WOC) by cucurbit[n]urils. in Dalton Transactions. 2012;41:12233.
doi:10.1039/C2DT31363D .

Iali, Wissam, Petrovic, Predrag V., Pfeffer, Michel, Grimme, Stefan, Djukic, Jean-Pierre, "The inhibition of iridium-promoted water oxidation catalysis (WOC) by cucurbit[n]urils" in Dalton Transactions, 41 (2012):12233,
https://doi.org/10.1039/C2DT31363D . .