| Affiliation: | 1. Institut für Chemie und Biochemie, Freie Universität Berlin, Fabeckstrasse 34–36, 14195 Berlin, Germany;2. Van't Hoff Institute of Molecular Sciences, Universiteit van Amsterdam, Science Park 904, 1090 GD Amsterdam, The Netherlands;3. Systèmes de Hautes Energies, Université Paul Sabatier, 118 route de Narbonne, 31062 Toulouse Cedex 9, France;4. Van't Hoff Institute of Molecular Sciences, Universiteit van Amsterdam, Science Park 904, 1090 GD Amsterdam, The Netherlands Department of Chemistry, Science Faculty, University of Johannesburg, P.O. Box 254, 2092 Auckland Park, Johannesburg, South Africa |
| Abstract: | A series of substituted phosphinines, 1-phosphabarrelenes and 5-phosphasemibullvalenes were synthesized and evaluated for their potential application as ligands in homogeneous catalytic reactions. While their buried volume (%Vbur) was calculated to get insight into the steric properties, [LNi(CO)3] complexes were prepared in order to determine the corresponding Tolman electronic parameter. ETS-NOCV (extended-transition-state natural orbital for chemical valence) calculations on [LAuCl] complexes further allowed an estimation of the σ- and π-contributions to the L− M interaction. AuI coordination compounds of selected examples were prepared and characterized by single crystal X-ray diffraction. Finally, the three classes of PIII compounds were successfully used in the AuI-catalyzed cycloisomerization of N-2-propyn-1-ylbenzamide, showing very good activities and selectivities, which are comparable with the reported data of cationic phosphorus-based gold catalysts. |
