Publication

Cationic Gold(I) Diarylallenylidene Complexes: Bonding Features and Ligand Effects

Sorbelli, D., Comprido, L. N. D. S., Knizia, G., Hashmi, A. S. K., Belpassi, L., Belanzoni, P. & Klein, J. E. M. N., 2-Jul-2019, In : Chemphyschem. 20, 13, p. 1671-1679 9 p.

Research output: Contribution to journalArticleAcademicpeer-review

Using computational approaches, we qualitatively and quantitatively assess the bonding components of a series of experimentally characterized Au(I) diarylallenylidene complexes (N.Kim, R.A.Widenhoefer, Angew. Chem. Int. Ed. 2018, 57, 4722-4726). Our results clearly demonstrate that Au(I) engages only weakly in pi-backbonding, which is, however, a tunable bonding component. Computationally identified trends in bonding are clearly correlated with the substitution patterns of the aryl substituents in the Au(I) diarylallenylidene complexes and good agreement is found with the previously reported experimental data, such as IR spectra, C-13 NMR chemical shifts and rates of decomposition together with their corresponding barrier heights, further substantiating the computational findings. The description of the bonding patterns in these complexes allow predictions of their spectroscopic features, their reactivity and stability.

Original languageEnglish
Pages (from-to)1671-1679
Number of pages9
JournalChemphyschem
Volume20
Issue number13
Publication statusPublished - 2-Jul-2019

    Keywords

  • allenylidene, computational chemistry, electronic structure, Gold, Lewis structures, TRANSITION-METAL-COMPLEXES, BASIS-SETS, CHEMICAL VALENCE, BACK-DONATION, AB-INITIO, CARBENE, ENERGY, APPROXIMATION, CATALYSIS, ORBITALS

Download statistics

No data available

ID: 102041727