241152-08-9Relevant articles and documents
Synthesis, structural characterization and catalytic activity of indenyl complexes of ruthenium bearing fluorinated phosphine ligands
Stark, Matthew J.,Shaw, Michael J.,Fadamin, Arghavan,Rath, Nigam P.,Bauer, Eike B.
, p. 41 - 53 (2017/09/12)
The synthesis, characterization and catalytic activity of new ruthenium complexes of fluorinated triarylphosphines is described. The new ruthenium complexes [RuCl(ind)(PPh3){P(p-C6H4CF3)3}] and [RuCl(ind)(PPh3){P(3,5-C6H3(CF3)2)3}] were synthesized in 57% and 24% isolated yield, respectively, by thermal ligand exchange of [RuCl(ind)(PPh3)2], where ind = indenyl ligand η5-C9H7?. The electronic and steric properties of the new complexes were studied through analysis of the X-ray structures and through cyclic voltammetry. The new complexes [RuCl(ind)(PPh3){P(p-C6H4CF3)3}] and [RuCl(ind)(PPh3){P(3,5-C6H3(CF3)2)3}] and the known complex [RuCl(ind)(PPh3)2}] differed only slightly in their steric properties, as seen from comparison of bond lengths and angles associated with the ruthenium center. As determined by cyclic voltammetry, the redox potentials of [RuCl(ind)(PPh3){P(p-C6H4CF3)3}] and [RuCl(ind)(PPh3){P(3,5-C6H3(CF3)2)3}] are +0.173 and + 0.370 V vs. Cp2Fe0/+, respectively, which are substantially higher than that of [RuCl(ind)(PPh3)2] (?0.023 V). After activation through chloride abstraction, the new complexes are catalytically active in the etherification of propargylic alcohols (8–24 h at 90 °C in toluene, 1–2 mol% catalyst loading, 29–61% isolated yields). As demonstrated by a comparative study for a test reaction, the three precursor complexes [RuCl(ind)(PPh3){P(p-C6H4CF3)3}], [RuCl(ind)(PPh3){P(3,5-C6H3(CF3)2)3}] and [RuCl(ind)(PPh3)2}] differed only slightly in catalytic activity.
New mononuclear ruthenium complexes of η5-cyclichydrocarbon containing azine ligands: Syntheses, spectral and structural studies
Singh, Keisham Sarjit,Mozharivskyj, Yurij A.,Th?ne, Carsten,Kollipara, Mohan Rao
, p. 3720 - 3729 (2007/10/03)
A series of mononuclear indenyl and pentamethylcyclopentadienyl ruthenium(II) complexes of formulation [(η5-L3) Ru(PPh3)(L2)]X, (where L3 = indenyl, pentamethylcyclopentadienyl; X = PF6 or BF4 and L 2 = azine ligands) have been prepared by the reaction of [(η5-L3)Ru(PPh3)2(CH 3CN)]X with the appropriate azine ligands in methanol or dichloromethane/benzene mixture. The reaction of nitro substituted azine ligands with the complexes [(η5-L3)Ru(PPh3) 2(CH3CN)]X are solvent dependent. All these complexes were isolated as their PF6 or BF4 salts. The complexes were fully characterized with the help of microanalyses, FT-IR and NMR spectroscopy. The molecular structure of representative complexes 5c and 6a were established by single X-ray crystallography.
Synthesis and characterization of [(Cp*)Ru(PPh3)(N-base)]X and [(η5-C9H7)Ru(PPh3)(N-base)]X complexes (see abstract)
Rao, Kollipara Mohan,Rymmai, Evergreen K.
, p. 307 - 312 (2008/10/08)
The reactions of [(η5-Cp*)Ru(PPh3)2 (CH3CN)]X (1) and [(η5-indenyl)Ru(PPh3)2 (CH3CN)]X (2) (η5-Cp* = η5-C5Me5; η5- indenyl = η5-C9H7; X = BF4 or PF6) with 2,2′-bipyridine (bipy.) and 1,10-phenanthroline (phen.) in benzene or toluene yielded complexes of the type [(η5-Cp*)Ru(PPh3)(L2)]X where L2 = bipy, X=BF4 (3) and L2=phen, X=PF6 (4); [(η5-indenyl)Ru(PPh3)2(L2)]X where L2 = bipy, X = PF6 (5) and L2 = phen, X = PF6 (6). Complex 6 has been established by single crystal X-ray diffraction analysis. Complex 6 crystallizes in the monoclinic space group P 21/c, with a = 14.6020 (12), b = 12.7100 (17) and c = 18.981 (2) A?, β = 98.982 (9)°, V = 3479.5 (7) A?3 and Z = 4. These complexes can also be prepared from reactions of [(η5- Cp*)Ru(PPh3)2Cl] (7) and [(η5-indenyl)Ru(PPh3)2Cl] (8) with the corresponding ligands in the presence of NH4PF6 or NH4BF4 in toluene. All the complexes were characterized by spectral and analytical data.
