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Reactions of [Ru(CO) 3 Cl 2 ] 2 with aromatic nitrogen donor ligands in alcoholic media
Author(s) -
Moreno M. Andreina,
Haukka Matti,
Kallinen Mirja,
Pakkanen Tapani A.
Publication year - 2006
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.1010
Subject(s) - chemistry , ruthenium , denticity , reactivity (psychology) , ligand (biochemistry) , medicinal chemistry , catalysis , chelation , alkoxy group , bridging ligand , inorganic chemistry , organic chemistry , alkyl , molecule , crystal structure , medicine , biochemistry , alternative medicine , receptor , pathology
The reactions of mono‐ and bidentate aromatic nitrogen‐containing ligands with [Ru(CO) 3 Cl 2 ] 2 in alcohols have been studied. In alcoholic media the nitrogen ligands act as bases promoting acidic behaviour of alcohols and the formation of alkoxy carbonyls [Ru(N–N)(CO) 2 Cl(COOR)] and [Ru(N) 2 (CO) 2 Cl(COOR)]. Other products are monomers of type [Ru(N)(CO) 3 Cl 2 ], bridged complexes such as [Ru(CO) 3 Cl 2 ] 2 (N), and ion pairs of the type [Ru(CO) 3 Cl 3 ] − [Ru(N–N)(CO) 3 Cl] + (N–N = chelating aromatic nitrogen ligand, N = non‐chelating or bridging ligand). The reaction and the product distribution can be controlled by adjusting the reaction stoichiometry. The reactivity of the new ruthenium complexes was tested in 1‐hexene hydroformylation. The activity can be associated with the degree of stability of the complexes and the ruthenium–ligand interaction. Chelating or bridging nitrogen ligands suppresses the activity strongly compared with the bare ruthenium carbonyl chloride, while the decrease in activity is less pronounced with monodentate ligands. A plausible catalytic cycle is proposed and discussed in terms of ligand–ruthenium interactions. The reactivity of the ligands as well as the catalytic cycle was studied in detail using the computational DFT methods. Copyright © 2005 John Wiley & Sons, Ltd.