| 14673857 |
Miqueu K, Despagnet-Ayoub E, Dyer PW, Bourissou D, Bertrand G: Theoretical study of rhodium (I) carbene complexes: the structural versatility of phosphino- compared with aminocarbenes. Chemistry. 2003 Dec 5;9(23):5858-64.
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) eta (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 eta (2)-complexes 10-18. These results as a whole emphasize the structural versatility of phosphino- compared with aminocarbene complexes. |
81(1,1,1,1) |