244766-40-3Relevant academic research and scientific papers
Ruthenium(II) Complexes with η6-Coordinated 3-Phenylpropanol and 2-Phenylethanol as Catalysts for the Tandem Isomerization/Claisen Rearrangement of Diallyl Ethers in Water
Lastra-Barreira, Beatriz,Francos, Javier,Crochet, Pascale,Cadierno, Victorio
, p. 3465 - 3474 (2018/10/31)
A series of half-sandwich ruthenium(II) complexes containing η6-coordinated 2-phenylethanol and 3-phenylpropanol ligands, namely [RuCl2{η6-C6H5CH2(CH2)nCH2OH}(PR3)] (PR3 = PMe3, PPh3, P(OMe)3, P(OEt)3, P(OiPr)3, P(OPh)3; n = 0 (1a-f), 1 (2a-f)), have been investigated as catalysts for the tandem isomerization/Claisen rearrangement of diallyl ethers into γ,δ-unsaturated aldehydes using, for the first time, water as solvent. The best results in terms of activity and regioselectivity were obtained with the 3-phenylpropanol derivative [RuCl2(η6-C6H5CH2CH2CH2OH){P(OEt)3}] (2d). Thus, using only 1 mol % of this complex, in combination with NaOH (2 mol %), different diallyl ethers could be conveniently converted into the corresponding aldehydes in high yields and short times under relatively mild thermal conditions (100 °C).
Ruthenium(II) complexes with ferrocene-modified arene ligands: Synthesis and electrochemistry
Therrien, Bruno,Vieille-Petit, Ludovic,Jeanneret-Gris, Julie,?těpni?ka, Petr,Süss-Fink, Georg
, p. 2456 - 2463 (2007/10/03)
A series of arene-ruthenium complexes of the general formula [RuCl2{η6-C6H5 (CH2)2R}L] with R=OH, CH2OH, OC(O)Fc, CH2OC(O)Fc (Fc=ferrocenyl) and L=PPh3, (diphenylphosphino)ferrocene, or bridging 1,1′-bis(diphenylphosphino)ferrocene, have been synthesized. Two synthetic pathways have been used for these ferrocene-modified arene-ruthenium complexes: (a) esterification of ferrocene carboxylic acid with 2-(cyclohexa-1,4-dienyl)ethanol, followed by condensation with RuCl3 · n H2O to afford [RuCl2 {η6-C6H5 (CH2)2OC(O)Fc}]2, and (b) esterification between ferrocene carboxylic acid and [RuCl2{η6 -C6H5(CH2)3OH}L] to give [RuCl2{η6-C6H5 (CH2)3OC(O)Fc}L]. All new compounds have been characterized by NMR and IR spectroscopy as well as by mass spectrometry. The single-crystal X-ray structure analysis of [RuCl2{η6-C6H5 (CH2)3OH}(PPh3)] shows that the presence of a CH2CH2CH2OH side-arm allows [RuCl2{η6-C6H5 (CH2)3OH}(PPh3)] to form an intramolecular hydrogen bond with a chlorine atom. The electrochemical behavior of selected representative compounds has been studied. Complexes with ferrocenylated side arms display the expected cyclic voltammograms, two independent reversible one-electron waves of the Ru(II)/Ru(III) and Fe(II)/Fe(III) redox couples. Introduction of a ferrocenylphosphine onto the ruthenium is reflected by an additonal reversible, one-electron wave due to ferrocene/ferrocenium system which is, however, coupled with the Ru(II)/Ru(III) redox system.
Synthesis and reaction of ruthenium(II) complexes containing heteroatom donor (O, N, and P) tethered to η6-arene ring
Miyaki, Yoshiharu,Onishi, Takafumi,Kurosawa, Hideo
, p. 369 - 377 (2008/10/08)
Synthesis of ruthenium(II) complexes chelated by the η6-arene ring and a pendent donor atom (O, N, and P) is described. The alcohol-containing η6-arene ruthenium complexes [Ru{η6-C6H5(CH2)3OH}(PR3)Cl2] (1a R=Ph; lb R = Et) and [Ru{η6C6H5(CH2)3OH}L2Cl]BF4 (2a L22,2'-bipyridine; 2b L2= 1,10-phenanthroline; 2c L22,2-bis[4(R)-phenyl-1,3-oxazolon-2-yl]propane, (R)-bpop) were prepared by treatment of [Ru{η6-C6H5(CH2)3OH}Cl2]2 with tertiary phosphines or N,N'-chelate ligands/NaBF4, respectively. Addition of 1 equiv. of AgBF4 to a solution of complexes 1 or 2 gave alcohol chelate complexes [Ru{η6:η1-C6H5(CH2)3OH}(PR3)Cl]BF4 (3a-b) or [Ru{η6:η1-C6H5(CH2)3OH}L2](BF4)2 (4a-c), respectively. Although stable in MeOH, the alcohol-Ru chelate bond of 3 and 4 was cleaved by Cl(min) ion. Treatment of 4 with bases (OH(min), R3N) led to abstraction of the hydroxy proton to give alkoxy chelate complexes [Ru{η6:η1-C6H5(CH2)3O}L2]BF4 (5a-c). In CH2Cl2 acidity of the hydroxy proton in 4c was revealed to be comparable to that of N-methylbenzylammonium cation (pK(a) in H2O, ca. 11). Amino chelate complexes [Ru{η6:η1-C6H5(CH2)(n)NH2}(PPh3)Cl]BF4 (Tan = 3; 7b n = 2) were prepared by treatment of ammonium complexes [Ru{η6-C6H5(CH2)(n)NH3Cl}(PPh3)Cl2] (6a n = 3; 6b n = 2) with 1 equiv. of NaOH and NaBF4. 7 were stable to the attack of Cl(min) ion. In contrast, the similar treatment of dimethylammonium derivative [Ru{η6-C6H5(CH2)3NMe2HCl}(PPh3)Cl2] (8) with KOH gave a non-chelate complex [Ru{η6-C6H5(CH2)3NMe2}(PPh3)Cl2] (9). Phosphorous chelate complexes [Ru{η6:η1-C6H5(CH2)3OPPR2}Cl2] (10a R=Ph; 10b R=(i)Pr) were prepared by reaction of [Ru{η6C6H5(CH2)3OH}Cl2]2, PPR2Cl, and EtN(i)Pr2. Treatment of 10b with AgBF4 and CO (1 atm) gave the cationic carbonyl complex [Ru{η6:η1-C6H5(CH2)3OP(i)Pr2}(CO)Cl]BF4 (11). (C) 2000 Elsevier Science S.A.
