| Affiliation: | 1. Dipartimento di Chimica, Biologia e Biotecnologie, Università degli Studi di Perugia, Via Elce di Sotto 8, 06123 Perugia, Italy;2. Molecular Inorganic Chemistry, Stratingh Institute for Chemistry Faculty of Science and Engineering, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The, Netherlands Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany;3. Department of Chemistry, Pennsylvania State University, 401A Chemistry Bldg;4. University Park, PA 16802, USA;5. Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany;6. Istituto di Scienze e Tecnologie Molecolari del CNR (CNR-ISTM) c/o Dipartimento di Chimica, Biologia e Biotecnologie, Università degli Studi di Perugia, via Elce di Sotto 8, Perugia, 06123 Italy;7. Molecular Inorganic Chemistry, Stratingh Institute for Chemistry Faculty of Science and Engineering, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The, Netherlands |
| Abstract: | 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 π-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, 13C 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. |
