Stacking interactions of aromatic ligands in transition metal complexes
Abstract
In this review article we present all the recent research on stacking interactions of aromatic ligands that coordinate to transition metals through their π-electrons (η-coordination). These studies were mostly based on searching the crystal structures from the Cambridge Structural Database (CSD) and on quantum chemical calculations. Stacking interactions between coordinated and uncoordinated benzene reach the energy of −4.40 kcal/mol, while the strongest calculated staking between two coordinated benzenes has the energy of −4.01 kcal/mol; this is significantly stronger than stacking between two uncoordinated benzenes (−2.73 kcal/mol). It was determined that in crystal structures both coordinated benzene and coordinated cyclopentadienyl anion form stacking interactions that dominantly have large horizontal displacements (more than 4.5 Å). This dominance is caused by the relatively strong stacking interactions at large displacements between benzene or Cp ligands in sandwich compounds, wh...ile for half-sandwich compounds they are supported by additional interactions of the other (usually branched) ligands. Larger aromatic ligands, tropylium and cyclooctatetraenide, almost exclusively form stacking interactions with large horizontal displacements. Methyl substituted benzene and Cp ligands dominantly form stacking interactions in combination with C–H/π interactions. Moreover, there is an interplay of stacking and aromatic C–H/π interactions in the CSD crystal structures, both interactions being important energy contributors to the stability of supramolecular systems. Stacking interactions of η-coordinated aromatic ligands are important in materials science, crystal engineering and medicinal chemistry, primarily in the application of ruthenium-arene complexes, where they determine the strength of bonding of these complexes to the DNA.
Keywords:
Benzene / Cyclopentadienyl / Half-sandwich compounds / Sandwich compounds / Stacking interactionsSource:
Coordination Chemistry Reviews, 2020, 419, 213338-Publisher:
- Elsevier
Funding / projects:
- Ministry of Science, Technological Development and Innovation of the Republic of Serbia, institutional funding - 200168 (University of Belgrade, Faculty of Chemistry) (RS-MESTD-inst-2020-200168)
- Qatar Foundation for Education, Science and Community Development
Note:
- Supplementary material: http://cherry.chem.bg.ac.rs/handle/123456789/4031
DOI: 10.1016/j.ccr.2020.213338
ISSN: 0010-8545
WoS: 000542181800002
Scopus: 2-s2.0-85085767144
Collections
Institution/Community
Hemijski fakultet / Faculty of ChemistryTY - JOUR AU - Malenov, Dušan P. AU - Zarić, Snežana D. PY - 2020 UR - https://cherry.chem.bg.ac.rs/handle/123456789/4030 AB - In this review article we present all the recent research on stacking interactions of aromatic ligands that coordinate to transition metals through their π-electrons (η-coordination). These studies were mostly based on searching the crystal structures from the Cambridge Structural Database (CSD) and on quantum chemical calculations. Stacking interactions between coordinated and uncoordinated benzene reach the energy of −4.40 kcal/mol, while the strongest calculated staking between two coordinated benzenes has the energy of −4.01 kcal/mol; this is significantly stronger than stacking between two uncoordinated benzenes (−2.73 kcal/mol). It was determined that in crystal structures both coordinated benzene and coordinated cyclopentadienyl anion form stacking interactions that dominantly have large horizontal displacements (more than 4.5 Å). This dominance is caused by the relatively strong stacking interactions at large displacements between benzene or Cp ligands in sandwich compounds, while for half-sandwich compounds they are supported by additional interactions of the other (usually branched) ligands. Larger aromatic ligands, tropylium and cyclooctatetraenide, almost exclusively form stacking interactions with large horizontal displacements. Methyl substituted benzene and Cp ligands dominantly form stacking interactions in combination with C–H/π interactions. Moreover, there is an interplay of stacking and aromatic C–H/π interactions in the CSD crystal structures, both interactions being important energy contributors to the stability of supramolecular systems. Stacking interactions of η-coordinated aromatic ligands are important in materials science, crystal engineering and medicinal chemistry, primarily in the application of ruthenium-arene complexes, where they determine the strength of bonding of these complexes to the DNA. PB - Elsevier T2 - Coordination Chemistry Reviews T1 - Stacking interactions of aromatic ligands in transition metal complexes VL - 419 SP - 213338 DO - 10.1016/j.ccr.2020.213338 ER -
@article{ author = "Malenov, Dušan P. and Zarić, Snežana D.", year = "2020", abstract = "In this review article we present all the recent research on stacking interactions of aromatic ligands that coordinate to transition metals through their π-electrons (η-coordination). These studies were mostly based on searching the crystal structures from the Cambridge Structural Database (CSD) and on quantum chemical calculations. Stacking interactions between coordinated and uncoordinated benzene reach the energy of −4.40 kcal/mol, while the strongest calculated staking between two coordinated benzenes has the energy of −4.01 kcal/mol; this is significantly stronger than stacking between two uncoordinated benzenes (−2.73 kcal/mol). It was determined that in crystal structures both coordinated benzene and coordinated cyclopentadienyl anion form stacking interactions that dominantly have large horizontal displacements (more than 4.5 Å). This dominance is caused by the relatively strong stacking interactions at large displacements between benzene or Cp ligands in sandwich compounds, while for half-sandwich compounds they are supported by additional interactions of the other (usually branched) ligands. Larger aromatic ligands, tropylium and cyclooctatetraenide, almost exclusively form stacking interactions with large horizontal displacements. Methyl substituted benzene and Cp ligands dominantly form stacking interactions in combination with C–H/π interactions. Moreover, there is an interplay of stacking and aromatic C–H/π interactions in the CSD crystal structures, both interactions being important energy contributors to the stability of supramolecular systems. Stacking interactions of η-coordinated aromatic ligands are important in materials science, crystal engineering and medicinal chemistry, primarily in the application of ruthenium-arene complexes, where they determine the strength of bonding of these complexes to the DNA.", publisher = "Elsevier", journal = "Coordination Chemistry Reviews", title = "Stacking interactions of aromatic ligands in transition metal complexes", volume = "419", pages = "213338", doi = "10.1016/j.ccr.2020.213338" }
Malenov, D. P.,& Zarić, S. D.. (2020). Stacking interactions of aromatic ligands in transition metal complexes. in Coordination Chemistry Reviews Elsevier., 419, 213338. https://doi.org/10.1016/j.ccr.2020.213338
Malenov DP, Zarić SD. Stacking interactions of aromatic ligands in transition metal complexes. in Coordination Chemistry Reviews. 2020;419:213338. doi:10.1016/j.ccr.2020.213338 .
Malenov, Dušan P., Zarić, Snežana D., "Stacking interactions of aromatic ligands in transition metal complexes" in Coordination Chemistry Reviews, 419 (2020):213338, https://doi.org/10.1016/j.ccr.2020.213338 . .