Stacking interactions between ruthenium p-cymene complexes. Combined crystallographic and density functional study
Article (Accepted Version)
Metadata
Show full item recordAbstract
The Cambridge Structural Database search for stacking interactions between p-cymene (1-methyl-4-isopropylbenzene) ligands of transition metal (mostly ruthenium) complexes revealed three preferred interaction geometries, all with antiparallel orientation. The most frequent one involves both stacking of aromatic rings and C-H/π interactions of methyl substituents with aromatic rings, while the second most frequent has stacking of aromatic rings and C-H/π interactions of methyl groups of isopropyl substituents with aromatic rings. The results of CSD search are in agreement with DFT calculations of interaction energies, since all the preferred CSD geometries correspond to minima on potential energy curves. The strongest calculated interaction between p-cymene ligands of model complexes [Ru(p cym)Cl¬¬2(NH3)] corresponds to the most frequent geometry found in crystal structures, and it has the B97-D2/def2-TZVP interaction energy of -7.56 kcal/mol. This is significantly stronger than interact...ion between benzene ligands of [Ru(benzene)Cl¬¬2(NH3)] complexes (-3.93 kcal/mol), revealing that substituents increase interaction strength substantially. All interaction geometries and their relative strengths are in agreement with electrostatic potentials of the monomer complex.
Keywords:
p-cymene / stacking interactions / C-H/pi interactions / crystal engineering / CSD / electrostatic potentialsSource:
CrystEngComm, 2019, 21, 7204-7210Publisher:
- Royal Society of Chemistry
Funding / projects:
- Noncovalent interactions of pi-systems and their role in molecular recognition (RS-MESTD-Basic Research (BR or ON)-172065)
Note:
- This is the peer-reviewed version of the following article: Malenov, D. P.; Zarić, S. D. Stacking Interactions between Ruthenium: P -Cymene Complexes: Combined Crystallographic and Density Functional Study. CrystEngComm 2019, 21 (47), 7204–7210. https://doi.org/10.1039/c9ce01290g
DOI: 10.1039/C9CE01290G
ISSN: 1466-8033
WoS: 000507597200016
Scopus: 2-s2.0-85075914866
Collections
Institution/Community
Hemijski fakultet / Faculty of ChemistryTY - JOUR AU - Malenov, Dušan P. AU - Zarić, Snežana D. PY - 2019 UR - https://cherry.chem.bg.ac.rs/handle/123456789/3839 AB - The Cambridge Structural Database search for stacking interactions between p-cymene (1-methyl-4-isopropylbenzene) ligands of transition metal (mostly ruthenium) complexes revealed three preferred interaction geometries, all with antiparallel orientation. The most frequent one involves both stacking of aromatic rings and C-H/π interactions of methyl substituents with aromatic rings, while the second most frequent has stacking of aromatic rings and C-H/π interactions of methyl groups of isopropyl substituents with aromatic rings. The results of CSD search are in agreement with DFT calculations of interaction energies, since all the preferred CSD geometries correspond to minima on potential energy curves. The strongest calculated interaction between p-cymene ligands of model complexes [Ru(p cym)Cl¬¬2(NH3)] corresponds to the most frequent geometry found in crystal structures, and it has the B97-D2/def2-TZVP interaction energy of -7.56 kcal/mol. This is significantly stronger than interaction between benzene ligands of [Ru(benzene)Cl¬¬2(NH3)] complexes (-3.93 kcal/mol), revealing that substituents increase interaction strength substantially. All interaction geometries and their relative strengths are in agreement with electrostatic potentials of the monomer complex. PB - Royal Society of Chemistry T2 - CrystEngComm T1 - Stacking interactions between ruthenium p-cymene complexes. Combined crystallographic and density functional study VL - 21 SP - 7204 EP - 7210 DO - 10.1039/C9CE01290G ER -
@article{ author = "Malenov, Dušan P. and Zarić, Snežana D.", year = "2019", abstract = "The Cambridge Structural Database search for stacking interactions between p-cymene (1-methyl-4-isopropylbenzene) ligands of transition metal (mostly ruthenium) complexes revealed three preferred interaction geometries, all with antiparallel orientation. The most frequent one involves both stacking of aromatic rings and C-H/π interactions of methyl substituents with aromatic rings, while the second most frequent has stacking of aromatic rings and C-H/π interactions of methyl groups of isopropyl substituents with aromatic rings. The results of CSD search are in agreement with DFT calculations of interaction energies, since all the preferred CSD geometries correspond to minima on potential energy curves. The strongest calculated interaction between p-cymene ligands of model complexes [Ru(p cym)Cl¬¬2(NH3)] corresponds to the most frequent geometry found in crystal structures, and it has the B97-D2/def2-TZVP interaction energy of -7.56 kcal/mol. This is significantly stronger than interaction between benzene ligands of [Ru(benzene)Cl¬¬2(NH3)] complexes (-3.93 kcal/mol), revealing that substituents increase interaction strength substantially. All interaction geometries and their relative strengths are in agreement with electrostatic potentials of the monomer complex.", publisher = "Royal Society of Chemistry", journal = "CrystEngComm", title = "Stacking interactions between ruthenium p-cymene complexes. Combined crystallographic and density functional study", volume = "21", pages = "7204-7210", doi = "10.1039/C9CE01290G" }
Malenov, D. P.,& Zarić, S. D.. (2019). Stacking interactions between ruthenium p-cymene complexes. Combined crystallographic and density functional study. in CrystEngComm Royal Society of Chemistry., 21, 7204-7210. https://doi.org/10.1039/C9CE01290G
Malenov DP, Zarić SD. Stacking interactions between ruthenium p-cymene complexes. Combined crystallographic and density functional study. in CrystEngComm. 2019;21:7204-7210. doi:10.1039/C9CE01290G .
Malenov, Dušan P., Zarić, Snežana D., "Stacking interactions between ruthenium p-cymene complexes. Combined crystallographic and density functional study" in CrystEngComm, 21 (2019):7204-7210, https://doi.org/10.1039/C9CE01290G . .