Theoretical Study of Rhodium(I) Carbene Complexes: The Structural Versatility of Phosphino- Compared with Aminocarbenes

✍ Scribed by Karinne Miqueu; Emmanuelle Despagnet-Ayoub; Philip W. Dyer; Didier Bourissou; Guy Bertrand

• Publisher: John Wiley and Sons
• Year: 2003
• Tongue: English
• Weight: 188 KB
• Volume: 9
• Category: Article
• ISSN: 0947-6539
• DOI: 10.1002/chem.200304928

✦ Synopsis

Abstract

Density functional calculations are reported for complexes of general formula [(carbene)RhClL~2~] featuring model phosphino‐ and aminocarbenes. Both the cis and trans isomers of the rhodium(I) η^1^‐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→C~carbene~ 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 η^2^‐complexes 10–18. These results as a whole emphasize the structural versatility of phosphino‐ compared with aminocarbene complexes.