Exploring Phosphine Electronic Effects on Molybdenum Complexes: A Combined Photoelectron Spectroscopy and Energy Decomposition Analysis Study

Dossmann, Héloïse; Gatineau, David; Clavier, Hervé; Memboeuf, Antony; Lesage, Denis; Gimbert, Yves

doi:10.1021/acs.jpca.0c06746

Cited by 6 publications

(2 citation statements)

References 95 publications

(167 reference statements)

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“…Furthermore, Rocchigiani and Bochmann used the 1 H NMR chemical shift of hydride ligands in organogold(III) complexes to study the trans - and cis -influence of various ligands, including (C^N), (C^C), (C^N^C), and (C^C^N) chelates . Eventually, gas-phase studies have also been involved in this field with, for instance, the use of ionization energies − or bond-dissociation energies (BDEs) , as descriptors of the ligand electronic effects. Recently, our group was thus implicated in a project aiming at the evaluation of the ligand strengths in a series of [L-Au-CO] + complexes (L being a phosphine, phosphite, or NHC ligand) using Au–CO BDEs determined by two mass spectrometry (MS)-based methodologies, blackbody infrared radiative dissociation (BIRD) and collision-induced dissociation (CID), in the multi-collisional regime .…”

Section: Introductionmentioning

confidence: 99%

Bond-Dissociation Energies to Probe Pyridine Electronic Effects on Organogold(III) Complexes: From Methodological Developments to Application in π-Backdonation Investigation and Catalysis

Bourehil,

Soep,

Seng

et al. 2023

Inorg. Chem.

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In this work, we report on the synthesis of several organogold(III) complexes based on 4,4′-diterbutylbiphenyl (C^C) and 2,6-bis(4-terbutylphenyl)pyridine (C^N^C) ligands and bond with variously substituted pyridine ligands (pyrR). Altogether, 33 complexes have been prepared and studied with mass spectrometry using higher-energy collision dissociation (HCD) in an Orbitrap mass spectrometer. A complete methodology including the kinetic modeling of the dissociation process based on the Rice− Ramsperger−Kassel−Marcus (RRKM) statistical method is proposed to obtain critical energies E 0 of the pyrR loss for all complexes. The capacity of these E 0 values to describe the pyridine ligand effect is further explored, at the same time as more classical descriptors such as 1 H pyridinic NMR shift variation upon coordination and Au−N pyrR bond length measured by X-ray diffraction. An extensive theoretical work, including density functional theory (DFT) and domain-based local pair natural orbital coupled-cluster theory (DLPNO-CCSD(T)) methods, is also carried out to provide bond-dissociation energies, which are compared to experimental results. Results show that dissociation energy outperforms other descriptors, in particular to describe ligand effects over a large electronic effect range as seen by confronting the results to the pyrR pK a values. Further insights into the Au−N pyrR bond are obtained through an energy decomposition analysis (EDA) study, which confirms the isolobal character of Au + with H + . Finally, the correlation between the lability of the pyridine ligands toward the catalytic efficiency of the complexes could be demonstrated in an intramolecular hydroarylation reaction of alkyne. The results were rationalized considering both pre-catalyst activation and catalyst reactivity. This study establishes the possibility of correlating dissociation energy, which is a gas-phase descriptor, with condensed-phase parameters such as catalysis efficiency. It therefore holds great potential for inorganic and organometallic chemistry by opening a convenient and easy way to evaluate the electronic influence of a ligand toward a metallic center.

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Section: Introductionmentioning

confidence: 99%

Bond-Dissociation Energies to Probe Pyridine Electronic Effects on Organogold(III) Complexes: From Methodological Developments to Application in π-Backdonation Investigation and Catalysis

Bourehil,

Soep,

Seng

et al. 2023

Inorg. Chem.

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“…In this study, we have used a range of realistic ligands including monophosphine (PPh 3 ), diphosphine (DPPE), phosphite (P(OMe) 3 ), and N-heterocyclic carbenes (dimethylimidazole, abbreviated as DMI) with a large variation in the electronic and steric properties. A description of the ligand–metal fragment bonding was established for quantitative analysis of σ-donation and π-back-donation contribution via energy decomposition analysis (EDA) and extended transition state-natural orbitals for chemical valence (ETS-NOCV). − We also examined the electron interaction characteristics and coordination number on the variation of energy barriers and mechanistic pathways for the formaldehyde hydroformylation.…”

Section: Introductionmentioning

confidence: 99%

Computational Insight into the Ligand Effect on the Original Activity of Rh-Catalyzed Formaldehyde Hydroformylation

Wei

Ding

et al. 2021

J. Phys. Chem. C

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This study performs a computational examination of the effect of the ligand nature on the Rh–L interaction and of the formaldehyde hydroformylation for substituted rhodium–carbonyl catalysts using a range of realistic mono- and bidentate ligands (CO, P(OMe)3, PPh3, DMI, and DPPE). The energy decomposition analysis of the Rh–L bond suggests the bidentate ligand, DPPE, shows the strongest interaction with Rh. The π-accepting capacity of monodentate ligands follows the sequence CO > P(OMe)3 > PPh3 > DMI. Analysis of the potential energy surface reveals the σ-donor ligands serve to increase the energy of the active anionic complex [Rh(CO)3L]−. No clear correlation has been found between the CO insertion/hydrogenolysis energy barrier and electronic properties of ligands, while the H2 oxidative addition barrier increases with increasing the ligand’s electron donating capacity. The investigation on the effect of the ligand (PPh3) coordination number demonstrates that the three-coordinated catalyst exhibits the highest energy barrier, and the influence of ligand steric hindrance on the H2 oxidative addition can be ignorable.

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Advancing Heterogeneous Organic Synthesis With Coordination Chemistry‐Empowered Single‐Atom Catalysts

Ye,

Li,

Zhang

et al. 2024

Advanced Materials

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For traditional metal complexes, intricate chemistry is required to acquire appropriate ligands for controlling the electron and steric hindrance of metal active centers. Comparatively, the preparation of single‐atom catalysts is much easier with more straightforward and effective accesses for the arrangement and control of metal active centers. The presence of coordination atoms or neighboring functional atoms on the supports' surface ensures the stability of metal single‐atoms and their interactions with individual metal atoms substantially regulate the performance of metal active centers. Therefore, the collaborative interaction between metal and the surrounding coordination environment enhances the initiation of reaction substrates and the formation and transformation of crucial intermediate compounds, which imparts single‐atom catalysts with significant catalytic efficacy, rendering them a valuable framework for investigating the correlation between structure and activity, as well as the reaction mechanism of catalysts in organic reactions. Herein, comprehensive overviews of the coordination interaction for both homogeneous metal complexes and single‐atom catalysts in organic reactions are provided. Additionally, reflective conjectures about the advancement of single‐atom catalysts in organic synthesis are also proposed to present as a reference for later development.

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Exploring Phosphine Electronic Effects on Molybdenum Complexes: A Combined Photoelectron Spectroscopy and Energy Decomposition Analysis Study

Cited by 6 publications

References 95 publications

Bond-Dissociation Energies to Probe Pyridine Electronic Effects on Organogold(III) Complexes: From Methodological Developments to Application in π-Backdonation Investigation and Catalysis

Bond-Dissociation Energies to Probe Pyridine Electronic Effects on Organogold(III) Complexes: From Methodological Developments to Application in π-Backdonation Investigation and Catalysis

Computational Insight into the Ligand Effect on the Original Activity of Rh-Catalyzed Formaldehyde Hydroformylation

Advancing Heterogeneous Organic Synthesis With Coordination Chemistry‐Empowered Single‐Atom Catalysts

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