215258-73-4Relevant academic research and scientific papers
Sequential C-H and C-Ru bond formation and cleavage during the thermally induced rearrangement of aryl ruthenium(II) complexes with [C6H3(CH2NMe2)2-2,6] - as a bidentate η2-C,N coordinated ligand. the crystal structures of the isomeric pairs [RuCl{η6-C10H14}
Steenwinkel, Pablo,James, Stuart L.,Gossage, Robert A.,Grove, David M.,Kooijman, Huub,Smeets, Wilberth J. J.,Spek, Anthony L.,Van Koten, Gerard
, p. 4680 - 4693 (1998)
New air-stable ruthenium(II) complexes that contain the aryldiamine [C6H3(CH2-NMe2) 2-2,6]- (NCN) are described. These complexes are [RuCl{η2-C,N-C6H3(CH2Me 2)2-2,6}(η6-C10H14)] (2; C10H14 = p-cymene = C6H4Me-iPr-4), [Ru{η2-C,N-C6H3(CH2NMe 2)2-2,6}(η5-C5H 5)(PPh3)] (5), and their isomeric forms [RuCl{η2-C,N-C6H3(CH2NMe 2)2-2,4}(η6-C10H14)] (3) and [Ru{η2-C,N-C6H3(CH2NMe 2)2-2,4}(η5-C5H 5)(PPh3)] (6), respectively Complex 2 has been prepared from the reaction of [Li(NCN)]2 with [RuCl2(η6-C10H14)]2, whereas complex 5 has been prepared by the treatment of [RuCl{η3-N,C,N-C6H3(CH2NMe 2)2-2,6}(PPh3)] (4) with [Na(C5H5)]n. Both 2 and 5 are formally 18-electron ruthenium(II) complexes in which the monoanionic potentially tridentate coordinating ligand NCN is η2-C,N-bonded. In solution (halocarbon solvent at room temperature or in aromatic solvents at elevated temperature), the intramolecular rearrangements of 2 and 5 afford complexes 3 and 6, respectively. This is a result of a shift of the metal-Caryl bond from position-1 to position-3 on the aromatic ring of the NCN ligand. The mechanism of the isomerization is proposed to involve a sequence of intramolecular oxidative addition and reductive elimination reactions of both aromatic and aliphatic C-H bonds. This is based on results from deuterium labeling, spectroscopic studies, and some kinetic experiments. The mechanism is proposed to contain fully reversible steps in the case of 5, but a nonreversible step involving oxidative addition of a methyl NCH2-H bond in the case of 2. The solid-state structures of complexes 2, 3, 5, and 6 have been determined by single-crystal X-ray diffraction. A new dinuclear 1,4-phenylene-bridged bisruthenium(II) complex, [1,4-{RuCl(η6-C10H14)}2{C 6(CH2NMe2) 4-2,3,5,6-C,N,C′,N′}] (9) has also been prepared from the dianionic ligand [C6(CH2NMe2)4-2,3,5,6]2- (C2N4). The C2N4 ligand is in an η2-C,N-η2-C′,N′-bis(bidentate) bonding mode. Compound 9 does not isomerize in solution (halocarbon solvent), presumably because of the absence of an accessible Caryl-H bond. Complex 9 could not be isolated in an analytically pure form, probably because of its high sensitivity to air and very low solubility, which precludes recrystallization.
