TY - JOUR
T1 - Mechanistic theoretical insight of Ru(II) catalysts with a meridional-facial bpea fashion competition
AU - Poater, Albert
AU - Mola, Joaquim
AU - Saliner, Ana Gallegos
AU - Romero, Isabel
AU - Rodríguez, Montserrat
AU - Llobet, Antoni
AU - Solà, Miquel
PY - 2008/5/22
Y1 - 2008/5/22
N2 - A novel mechanistic insight for the interconversion between two octahedral ruthenium isomers, trans-mer-[RuIICl2(bpea)(dmso)], 2a, and cis-fac-[RuIICl2(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. © 2008 Elsevier B.V. All rights reserved.
AB - A novel mechanistic insight for the interconversion between two octahedral ruthenium isomers, trans-mer-[RuIICl2(bpea)(dmso)], 2a, and cis-fac-[RuIICl2(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. © 2008 Elsevier B.V. All rights reserved.
U2 - 10.1016/j.cplett.2008.04.110
DO - 10.1016/j.cplett.2008.04.110
M3 - Article
SN - 0009-2614
VL - 458
SP - 200
EP - 204
JO - Chemical Physics Letters
JF - Chemical Physics Letters
IS - 1-3
ER -