133270-66-3Relevant academic research and scientific papers
Synthesis, characterization, and reactivity of ruthenium carbonyl complexes containing a chelating triphosphine ligand and two weakly coordinated anions
Blosser, Patrick W.,Gallucci, Judith C.,Wojcicki, Andrew
, p. 2376 - 2384 (2008/10/08)
Protonation of cis-mer-RuH2(CO)(Cyttp) (Cyttp = PhP(CH2CH2CH2PCy2)2) with excess HX (X = BF4, O3SCF3) in benzene/diethyl ether produces air-stable complexes with two weakly coordinated anions, viz., cis-mer-RuX2(CO)(Cyttp) (X = BF4 (2), O3SCF3 (3)). A single-crystal X-ray diffraction analysis at 223 K shows that 3 crystallizes in the space group P21/c with cell parameters a = 11.712 (2) ?, b = 15.338 (2) ?, c = 27.072 (3) ?, β = 98.58 (1)°, Z = 4, V = 4809 (1) ?3, R = 0.041, and Rw = 0.046 for the 7036 intensities with Fo2 > 3σ(Fo2) and the 539 variables. The molecules contain two cis-oriented monodentate O3SCF3- ligands. The structural behavior of 2 and 3 in both CD2Cl2 and acetone-d6 was investigated by variable-temperature 31P{1H} and 19F{1H} NMR spectroscopies in the range 178-303 K; a complex behavior involving species with coordinated and free BF4- and O3SCF3- ions was observed. 2 and 3 are useful synthons for a variety of coordination and organometallic complexes. 2 undergoes substitution reactions with acetonitrile and organic isocyanides to afford disubstituted complexes cis-mer-[Ru(CO)L2(Cyttp)][BF4]2 (L = MeCN, CNBu-t, CNCy). New Ru-F complexes [Ru(F)(CO)(L)-(Cyttp)][BF4] (L = H2O, CO, CNBu-t) have also been synthesized from 2. The absence of fluoride abstraction from triflate and the solubility of 3 in THF render this a more versatile starting material than 2. Substitution reactions with acetonitrile and ammonia produce disubstituted complexes cis-mer-[Ru(CO)L2(Cyttp)][O3SCF3]2 (L = MeCN, NH3). The reaction of 3 with an excess of trimethyl phosphite leads only to the monosubstituted phosphite products [Ru(CO)(P(OMe)3)(Cyttp)][O3SCF3]2 (11a, 11b), which probably differ by the orientation of the Ph group of Cyttp. Complexes with the cations [Ru(X)(CO)(P-(OMe)3)(Cyttp)]+ (X = Cl, OMe) are generated from reactions of mixtures of 11a and 11b with the appropriate anion. 3 also reacts with selected anions (X- = Me-, I-, and H-) to afford complexes cis-mer-RuX2(CO)(Cyttp).
Synthesis and reactivity of ruthenium hydride complexes containing chelating triphosphines. 4. Reactions of ruthenium hydride complexes containing triphosphines with olefins
Jia, Guochen,Meek, Devon W.,Gallucci, Judith C.
, p. 2549 - 2555 (2008/10/08)
Methyl vinyl ketone reacts with RuH(BH4)(triphos) (triphos = ttp, Cyttp) to give Ru(η4-CH2= CHCOMe)(triphos). The compound Ru(η4-CH2=CHCOMe)(Cyttp) is also formed from the reaction of RuH4(Cyttp) with methyl vinyl ketone. RuH4(Cyttp) reacts with 2-vinylpyridine to produce two isomers of RuH(CH=CHC5H4N)(Cyttp), with vinyl acetate to give RuH(O2CMe)(Cyttp), and with methyl acrylate to yield RuH2(CO)(Cyttp). The reaction products were characterized by multinuclear NMR and IR spectroscopy. The structure of Ru(η4-CH2=CHCOMe)(ttp) has been confirmed by single-crystal X-ray diffraction. Ru(η4-CH2=CHCOMe)(ttp) crystallizes in the space group P21/c with cell parameters a = 10.236 (1) A?, b = 20.845 (3) A?, c = 16.922 (2) A?, β = 106.58 (1)°, Z = 4, V = 3460 A?3, R = 0.031, and Rw = 0.038 for the 5829 intensities with Fo2 > 3σ(Fo2) and the 418 variables.
