Heterobimetallic 21,23-dimetallaporphyrin: activation of metal–metal interactions within the porphyrinoid macrocycle

Vetter, Grzegorz; Białońska, Agata; Jezierska, Aneta; Panek, Jarosław J.; Pacholska‐Dudziak, Ewa

doi:10.1039/d3cc01367g

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“…In particular, we focused on the analysis on two specific catalytic features of the system: (a) the non-innocent ligands at the Ru site and (b) their influence on the electronic structure of the complexes. Porphyrins belong to a group of naturally occurring macrocyclic compounds, that gave rise to synthesis and research on new compounds obtained under laboratory conditions, e. g. [35][36][37][38][39][40][41] They are key components in chemical reactions, e. g. catalytic activity in many reactions and enzymes. [42][43][44] This is the main reason why the derivatives of porphyrins -metalloporphyrin complexes were considered to be promising in the reaction of partial oxidation of CH 4 .…”

Section: Introductionmentioning

confidence: 99%

Partial Methane Oxidation to Methanol on Ru‐Porphyrins – on the Role of Non‐Innocent Ligands and Spin Crossover

Kizior,

Jezierska,

Szyja

2023

ChemPhysChem

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The partial oxidation reaction of CH4 led to the formation of CH3OH in the presence of Ru‐porphyrin oxo complexes (denoted as POR, POR‐O and POR‐OH where in the case of the last two, oxygen atom and the OH group were attached to the active site, respectively), in which Ru was present on different oxidation states. The simulations were performed based on Density Functional Theory (DFT) with extended geometric and electronic structure analyses of each reaction step. Moreover, the reaction pathways were investigated in different spin states. The Spin Crossover (SCO) phenomenon was found to play an important role in the kinetics of the reaction in the presence of POR and POR‐O. Harmonic Oscillator Model of Aromaticity (HOMA) index was applied for different spin states to estimate the aromaticity changes of the pyrrole rings in the Ru‐porphyrin complexes. In order to characterize the nature of bonding, the Natural Bond Orbitals (NBO) analysis including the Wiberg Bond Index (WBI) and Natural Population Analysis (NPA) was carried out. Finally, the Non‐Covalent Interactions (NCI) index was employed to gain insight into interactions between the components of the reaction. It was found that the non‐covalent interactions cannot be neglected in the studied reaction paths.

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Section: Introductionmentioning

confidence: 99%

Partial Methane Oxidation to Methanol on Ru‐Porphyrins – on the Role of Non‐Innocent Ligands and Spin Crossover

Kizior,

Jezierska,

Szyja

2023

ChemPhysChem

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Heterobimetallic 21,23-dimetallaporphyrin: activation of metal–metal interactions within the porphyrinoid macrocycle

Abstract: The incorporation of two metal atoms, platinum and rhodium, in place of NH groups in the porphyrin macrocycle brings them into close proximity. The weak metal–metal bond is switched on and off depending on the oxidation state of the platinum ion.

Cited by 1 publication

References 28 publications

Partial Methane Oxidation to Methanol on Ru‐Porphyrins – on the Role of Non‐Innocent Ligands and Spin Crossover

Partial Methane Oxidation to Methanol on Ru‐Porphyrins – on the Role of Non‐Innocent Ligands and Spin Crossover

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