Synthesis and characterization of triosmium and triruthenium pyrene clusters

Arce, Alejandro J.; Cañavera, Farrah; Sanctis, Ysaura De; Ascanio, Julián; Machado, Rubén; González, Teresa

doi:10.1016/j.jorganchem.2009.01.013

Cited by 9 publications

(8 citation statements)

References 20 publications

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“…The pyryne ligand in 9 is coordinated to the cluster at its 4 and 5 positions, which is similar to that of a previously reported pyryne compound, Os 3 (CO) 9 (μ 3 -4,5-C 16 H 9 )(μ-H) 2 , except for the presence of the bridging AuPPh 3 in place of one of the bridging hydride ligands . The pyryne C–C bond distance (C46–C47 = 1.419(9) Å) is similar in length to that found in the aryne ligand in 6 , 7 , and 8 .…”

Section: Results and Discussionsupporting

confidence: 83%

Unsaturated Triosmium Carbonyl Cluster Complexes with Bridging Aryl Ligands: Structures, Bonding, and Transformations

2013

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For the calculations on 2, geometry optimized calculations were performed with ADF2012 program 24 by using the PBEsol functional 1 with scalar relativistic correction and valence quadruple-ζ + 4 polarization, relativistically optimized (QZ4P) basis sets for osmium and gold and valence double-ζ function (DZ) basis sets for the phosphorus, carbon, oxygen, and hydrogen atoms with no frozen cores. The molecular orbitals for 2 and their energies were determined by a geometry optimized calculations that were initiated with the structures as determined from the crystal structure analyses. The fragment analysis for 2 was also performed with the ADF programs by using the meta-Generalized Gradient Approximation (meta-GGA) level nonempirical Tao-Perdew-Staroverov-Scuseria (TPSS) functional. 2 The phenyl group was used as one fragment and the other fragment was the complete molecule minus the phenyl group. The MOs of the fragments were then calculated by using the same basis sets as described above.For the calculations of 3b, geometry optimized calculations were performed with ADF2012 program 1 by using the PBEsol functional with scalar relativistic correction and valence triple-ζ +polarization, relativistically optimized (TZP) basis sets, with small frozen cores. The molecular orbitals and their energies were determined by geometry optimization

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Section: Results and Discussionsupporting

confidence: 83%

Unsaturated Triosmium Carbonyl Cluster Complexes with Bridging Aryl Ligands: Structures, Bonding, and Transformations

2013

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“…The crystal structure‘s geometry was extracted from the Crystallographic Information File (CCDC 708308) based on X‐ray diffraction experiments reported by Cañavera et al [2] . Validation of inter‐ and intra‐molecular interactions involved distance measurements between chemical entities using Diamond Crystal and Molecular Structure Visualization software [25] .…”

Section: Computational Detailsmentioning

confidence: 99%

“…The crystal structure's geometry was extracted from the Crystallographic Information File (CCDC 708308) based on X-ray diffraction experiments reported by Cañavera et al [2] Validation of inter-and intra-molecular interactions involved distance measurements between chemical entities using Diamond Crystal and Molecular Structure Visualization software. [25] Analysis of intermolecular interactions within the same unit cell and two adjacent unit cells utilized molecular motifs extracted from the Crystallographic Information File.…”

Section: Computational Details Intermolecular Interactionsmentioning

confidence: 99%

“…[23] In a previous work, one of the authors, F. Cañavera, synthesized Os 3 (CO) 9 (μ-H) 2 (μ 3 -η 1 : η 1 : η 2 -C 16 H 8 ) crystals as a model of chemisorbed species during hydrogenation. While the interaction analysis focused on intermediates and final products, [2] the inter-and intra-molecular interactions governing crystal formation remained unexplored. Hence, this study aims to analyze the crystal structure of the title molecule using reanalyzed X-ray crystallography while providing new insights from RDG, QTAIM, and NBO analyses.…”

Section: Introductionmentioning

confidence: 99%

“…Metal clusters have served as invaluable models for understanding the behavior of chemisorbed species on metal surfaces [1–5] . Consequently, various compounds have been synthesized to gain insights into the covalent and noncovalent interactions between molecules and metal clusters.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Insights into Unconventional Intramolecular CH⋅⋅⋅CO Interaction in Os₃(CO)₉(μ‐H)₂(μ³‐η¹: η¹: η²‐C₁₆H₈) Crystal: A QTAIM, NCI, and NBO Exploration

2023

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This work presents a study investigating the inter‐ and intra‐molecular interactions within the Os3(CO)9(μ‐H)2(μ3‐η1: η1: η2‐C16H8) crystal. The crystal‘s behavior is analyzed by comparing experimental distances, revealing intriguing interactions. In the isolated molecule, an unconventional pyrene‐C−H⋅⋅⋅CO interaction is observed, an electron transfer from σ(C−H) to π*(CO). Strikingly, the Quantum Theory of Atoms in Molecules identifies similarities to an intramolecular charge‐inverted hydrogen bond, despite its relatively low stability due to proximity to critical points. Energy surface scans demonstrate that the interaction arises from van der Waals strain induced by the crystal‘s packing structure. The proximity between carbonyl and pyrene facilitates electron transfer between σ(C−H) and π*(CO) at distances similar to the crystal structure. A significant correlation is established between total energy and the ratio (|V|/G) of potential energy density (V) to Lagrangian kinetic energy (G) at bond (BCP) and ring (RCP) critical points, underscoring the role of electron delocalization on the pseudo‐ring in determining the existence and characteristics of these interactions. In conclusion, this study provides valuable insights into molecular interactions within the Os3(CO)9(μ‐H)2(μ3‐η1: η1: η2‐C16H8) crystal, enriching our understanding of crystal interactions and offering perspectives for further exploration in this field.

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σ‐Bonded Transition Metal Complexes of Polycyclic Aromatic Carbon Compounds

Sharp

2011

Fragments of Fullerenes and Carbon Nanotubes

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Synthesis and characterization of triosmium and triruthenium pyrene clusters

Cited by 9 publications

References 20 publications

Unsaturated Triosmium Carbonyl Cluster Complexes with Bridging Aryl Ligands: Structures, Bonding, and Transformations

Unsaturated Triosmium Carbonyl Cluster Complexes with Bridging Aryl Ligands: Structures, Bonding, and Transformations

Insights into Unconventional Intramolecular CH⋅⋅⋅CO Interaction in Os₃(CO)₉(μ‐H)₂(μ³‐η¹: η¹: η²‐C₁₆H₈) Crystal: A QTAIM, NCI, and NBO Exploration

σ‐Bonded Transition Metal Complexes of Polycyclic Aromatic Carbon Compounds

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Synthesis and characterization of triosmium and triruthenium pyrene clusters

Cited by 9 publications

References 20 publications

Unsaturated Triosmium Carbonyl Cluster Complexes with Bridging Aryl Ligands: Structures, Bonding, and Transformations

Unsaturated Triosmium Carbonyl Cluster Complexes with Bridging Aryl Ligands: Structures, Bonding, and Transformations

Insights into Unconventional Intramolecular CH⋅⋅⋅CO Interaction in Os3(CO)9(μ‐H)2(μ3‐η1: η1: η2‐C16H8) Crystal: A QTAIM, NCI, and NBO Exploration

σ‐Bonded Transition Metal Complexes of Polycyclic Aromatic Carbon Compounds

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Insights into Unconventional Intramolecular CH⋅⋅⋅CO Interaction in Os₃(CO)₉(μ‐H)₂(μ³‐η¹: η¹: η²‐C₁₆H₈) Crystal: A QTAIM, NCI, and NBO Exploration