Theoretical Study of Rhodium(I) Carbene Complexes: The Structural Versatility of Phosphino- Compared with Aminocarbenes
- 5 December 2003
- journal article
- research article
- Published by Wiley in Chemistry – A European Journal
- Vol. 9 (23) , 5858-5864
- https://doi.org/10.1002/chem.200304928
Abstract
Density functional calculations are reported for complexes of general formula [(carbene)RhClL2] featuring model phosphino‐ and aminocarbenes. Both the cis and trans isomers of the rhodium(I) η1‐complexes (1–9) were investigated, and the influence of the rhodium co‐ligands (L=ethylene, phosphine, or carbon monoxide) was evaluated. In the case of phosphinocarbenes and carbon monoxide as a ligand, a somewhat unusual coordination mode was observed, in which a significant intramolecular Cl→Ccarbene interaction is present. The propensity of phosphino‐ and aminocarbenes to behave as four electron donors was also investigated both structurally and energetically on the related η2‐complexes 10–18. These results as a whole emphasize the structural versatility of phosphino‐ compared with aminocarbene complexes.Keywords
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