Mechanistic theoretical insight of Ru(II) catalysts with a meridional-facial bpea fashion competition

作者：Poater Albert^*; Mola Joaquim; Saliner Ana Gallegos; Romero Isabel; Rodriguez Montserrat; Llobet Antoni; Sola Miquel

来源：Chemical Physics Letters, 2008, 458(1-3): 200-204.

DOI：10.1016/j.cplett.2008.04.110

A novel mechanistic insight for the interconversion between two octahedral ruthenium isomers, trans-mer-[ Ru(II)Cl(2)(bpea)(dmso)], 2a, and cis-fac-[ Ru(II)Cl(2)(bpea)(dmso)], 2b, (bpea = N, N-bis(2-pyridylmethyl) ethylamine) is reported. The isomer 2a displaying the bpea ligand in a meridional fashion is kinetically favoured with respect to 2b, with the bpea ligand in a facial fashion, which is the thermodynamically favoured one. The dissociative mechanism with the cleavage of a chloro ligand as starting point becomes more feasible with respect to the intramolecular mechanism. However, DFT calculations make competitive the mechanism which dissociates first the dmso ligand. Thus, a further characterisation of all the reaction pathways for the interconversion 2a --> 2b has been fulfilled.

• 出版日期2008-6-6