6531-45-9Relevant academic research and scientific papers
Synthesis, Structure, and Reactivity of the Ethyl Yttrium Metallocene, (C5Me5)2Y(CH2CH3), Including Activation of Methane
MacDonald, Matthew R.,Langeslay, Ryan R.,Ziller, Joseph W.,Evans, William J.
, p. 14716 - 14725 (2015/12/09)
(C5Me5)2Y(μ-Ph)2BPh2, 1, reacted with ethyllithium at -15°C to make (C5Me5)2Y(CH2CH3), 2, which is thermally unstable at room temperature and formed the C-H bond activation product, (C5Me5)2Y(μ-H)(μ-n1:n5-CH2C5Me4)Y(C5Me5), 3, containing a metalated (C5Me5)1- ligand. Spectroscopic evidence for 2 was obtained at low temperature, and trapping experiments with iPrNCNiPr and CO2 gave the Y-CH2CH3 insertion products, (C5Me5)2Y[iPrNC(Et)NiPr-k2N,N′], 4, and [(C5Me5)2Y(μ-O2CEt)]2, 5. Although 2 is highly reactive, low temperature isolation methods allowed the isolation of single crystals which revealed an 82.6(2)°Y-CH2-CH3 bond angle consistent with an agostic structure in the solid state. Complex 2 reacted with benzene and toluene to make (C5Me5)2YPh, 7, and (C5Me5)2YCH2Ph, 8, respectively. The reaction of 2 with [(C5Me5)2YCl]2 formed (C5Me5)2Y(μ-Cl)(μ-n1:n5-CH2C5Me4)Y(C5Me5) in which a (C5Me5)1- ligand was metalated. C-H bond activation also occurred with methane which reacted with 2 to make [(C5Me5)2YMe]2, 9.
Formation of carboxylate complexes from the reactions of CO2 with ethylene complexes of molybdenum and tungsten. X-ray and neutron diffraction studies
Alvarez, Rafael,Carmona, Ernesto,Galindo, Agustín,Gutiérrez, Enrique,Marín, José M.,Monge, Angeles,Poveda, Manuel L.,Ruiz, Caridad,Savariault, Jean M.
, p. 2430 - 2439 (2008/10/08)
Carbon-carbon bond formation by coupling of ethylene with carbon dioxide on the coordination sphere of the metal center in the electron-rich complexes trans-M(C2H4)2(PMe3)4 (M = Mo, 1; M = W, 2) can be effected under mild conditions by reactions of 1 and 2 with CO2. These afford the binuclear hydrido acrylate derivatives [MH(OOCCH=CH2)(C2H4)(PMe3) 2]2 (M = Mo, 3; M = W, 4), which contain bridging μ2-η3,η1-acrylate ligands. Hydrogenation of 3 and 4 in the presence of PMe3 provides the hydrido propionates MoH(η2-OOCCH2CH3)(PMe3) 4 (5) and WH3(η1-OOCCH2CH3) (PMe3)4 (6), but the direct reaction of 1 and 2 with a 1:1 mixture of CO2/H2 yields instead the hydrido carbonate derivatives MH2(η2-CO3)(PMe3)4 (M = Mo, 7; M = W, 8). The hydrido allyl compounds MH(η3-C3H5)(PMe3)4 (M = Mo, 9; M = W, 10), formed by sodium amalgam reduction of MCl4(PMe3)3 under propylene, do not react with CO2 with carbon-carbon bond formation but rather with reductive elimination of propylene and production of the adduct transMo(CO2)2(PMe3)4 and various carbonate complexes. The crystal and molecular structures of 3, 4, and 6 have been determined by X-ray studies, and, in addition, a low-temperature (20 K) neutron diffraction analysis of 4 has been performed. 3 is monoclinic, P21/n, with a = 12.117 (8) A?, b = 15.072 (5) A?, c = 17.700 (5) A?, β = 102.18 (3)°, Z = 4, and R = 0.032, while 6 is monoclinic, P21/c, with a = 12.813 (2) A?, b = 8.903 (3) A?, c = 21.671 (3) A?, β = 88.62 (1)°, Z = 4, and R = 0.048. The crystal of 4 used for the neutron diffraction study is monoclinic, P21/c, with a = 14.23 (1) A?, b = 11.80 (1) A?, c = 20.58 (2) A?, β = 104.94 (6)°, Z = 4, and R = 0.034.
Relationship between the Electronic Structure of Acrylic and Methacrylic Acid and the Rates of Hydrogenation of Their Salts on Pt Black
Volkova, L. D.,Vyaznikovtseva, O. V.,Gabdrakipov, V. Z.,Sokol'skii, D. V.
, p. 1650 - 1652 (2007/10/02)
We have studied the hydrogenation of the alkali metal salt of acrylic and methacrylic acid on platinum black.The relative reactivities, which are interest in calculations of the electronic structure of acids, have been determined by the CNDO/2 method.
