809230-59-9Relevant academic research and scientific papers
η3-Edge-bridging versus η3-face-capping coordination of a conjugated ynenyl ligand on a triruthenium cluster core
Cabeza, Javier A.,Del Rio, Ignacio,Garcia-Granda, Santiago,Moreno, Marta,Perez-Carreno, Enrique,Suarez, Marta
, p. 5849 - 5855 (2004)
The reaction of the cluster complex [Ru3(μ-H) (μ3-η2-apyr)(CO)9] (1; Hapyr = 2-aminopyrimidine) with 1,6-diphenoxy-2,4-hexadiyne in refluxing THF gives the trinuclear derivative [Ru3(μ3-η2-apyr) (μ-η3-PhOCH2CH=CC≡CCH2OPh)(μ- CO)2(CO)6] (2), which contains an edgebridging ynenyl ligand. Heating 2 in refluxing toluene leads to an equilibrium mixture of compounds 2 and [Ru3(μ3η2-apyr) (μ3-η3-PhOCH2CH=CC≡CCH 2OPh)(CO)8] (3), in which the ynenyl ligand is in a face-capping position. A mechanistic proposal that accounts for the interconversion of 2 and 3 has been obtained from DFT calculations, which have also revealed that isomer 2 is slightly more stable than 3 (3.5 kcal/mol). The bonding of the ynenyl ligands of 2 and 3 to their corresponding triruthenium frameworks has been studied by MO calculations.
