The importance of the Dewar-Chatt-Duncanson model for inorganic chemists cannot be overstated. It provides a simple yet robust framework for understanding metal-ligand bonding in terms of sigma-donation and pi-back-donation. Some years ago, a publication (Chem. Eur. J. 2015, 21, 2467) introduced a method to effectively correlate experimental NMR data with back-donation, using [LAu(ADC)]+/0 complexes (ADC=acyclic diaminocarbene) as case study. Here, we theoretically expand the same method to [L(PH3)(ADC)PtCl]+/0 complexes, to verify whether the method is general and to gain deeper insights into the influence of L on Pt-ADC bonding, especially in the trans position. Such insights hold potential for guiding rational catalyst design strategies.The platinum-carbene bond components (in terms of donation/back-donation) are here quantified using the Charge Displacement analysis coupled with the Extended Transition State-Natural Orbital for Chemical Valence orbitals. These components are then compared with the rotational barrier of the C-N bond of the acyclic diaminocarbene used as probe, revealing a good linear correlation. image

Exploring the Pt→Ligand Back‐Donation Through the Rotational Barrier of an Acyclic Diaminocarbene

Simona Samaritani;Luca Labella;Gianluca Ciancaleoni
Ultimo
2024-01-01

Abstract

The importance of the Dewar-Chatt-Duncanson model for inorganic chemists cannot be overstated. It provides a simple yet robust framework for understanding metal-ligand bonding in terms of sigma-donation and pi-back-donation. Some years ago, a publication (Chem. Eur. J. 2015, 21, 2467) introduced a method to effectively correlate experimental NMR data with back-donation, using [LAu(ADC)]+/0 complexes (ADC=acyclic diaminocarbene) as case study. Here, we theoretically expand the same method to [L(PH3)(ADC)PtCl]+/0 complexes, to verify whether the method is general and to gain deeper insights into the influence of L on Pt-ADC bonding, especially in the trans position. Such insights hold potential for guiding rational catalyst design strategies.The platinum-carbene bond components (in terms of donation/back-donation) are here quantified using the Charge Displacement analysis coupled with the Extended Transition State-Natural Orbital for Chemical Valence orbitals. These components are then compared with the rotational barrier of the C-N bond of the acyclic diaminocarbene used as probe, revealing a good linear correlation. image
2024
Nerli, Francesca; Samaritani, Simona; Labella, Luca; Ciancaleoni, Gianluca
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11568/1273408
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