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- Title
<sup>13</sup>C NMR Spectroscopy of N-Heterocyclic Carbenes Can Selectively Probe σ Donation in Gold(I) Complexes.
- Authors
Marchione, Demian; Izquierdo, Maria A.; Bistoni, Giovanni; Havenith, Remco W. A.; Macchioni, Alceo; Zuccaccia, Daniele; Tarantelli, Francesco; Belpassi, Leonardo
- Abstract
The Dewar-Chatt-Duncanson (DCD) model provides a successful theoretical framework to describe the nature of the chemical bond in transition-metal compounds and is especially useful in structural chemistry and catalysis. However, how to actually measure its constituents (substrate-to-metal donation and metal-to-substrate back-donation) is yet uncertain. Recently, we demonstrated that the DCD components can be neatly disentangled and the π back-donation component put in strict correlation with some experimental observables. In the present work we make a further crucial step forward, showing that, in a large set of charged and neutral N-heterocyclic carbene complexes of gold(I), a specific component of the NMR chemical shift tensor of the carbenic carbon provides a selective measure of the σ donation. This work opens the possibility of 1) to characterize unambiguously the electronic structure of a metal fragment (LAu(I) n+/0 in this case) by actually measuring its σ-withdrawing ability, 2) to quickly establish a comparative trend for the ligand trans effect, and 3) to achieve a more rigorous control of the ligand electronic effect, which is a key aspect for the design of new catalysts and metal complexes.
- Subjects
CARBENES; CARBON compounds spectra; TRANSITION metal compounds synthesis; GOLD compound synthesis; GOLD compounds; TRANSITION metal compounds spectra; HETEROCYCLIC compounds synthesis; CHEMICAL bonds; NUCLEAR magnetic resonance spectroscopy
- Publication
Chemistry - A European Journal, 2017, Vol 23, Issue 11, p2722
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201605502