Homobinuclear Ru-Ru and heterobinuclear Ru-Rh complexes with alkynyl and vinylidene ligands as molecular units

2001 ◽  
Vol 79 (5-6) ◽  
pp. 519-524 ◽  
Author(s):  
Helmut Werner ◽  
Petra Bachmann ◽  
Marta Martin

The chelate complex [RuCl2{κ2(P,O)-i-Pr2PCH2CH2OMe}2] (1) reacted, in the presence of CF3SO3Ag, with 1 equiv of C6H4(CºCH)2-p (4) to afford the mononuclear vinylidene compound [RuCl(C=CHC6H4-p-CºCH){κ2(P,O)-i-Pr2PCH2CH2OMe}2](CF3SO3) (3). From 1 and 0.5 equiv of 4, the binuclear bis(vinylidene) complex [RuCl{κ2(P,O)-i-Pr2PCH2CH2OMe}2(C=CHC6H4-p-CH=C)RuCl{κ2(P,O)-i-Pr2PCH2CH2OMe}2](CF3SO3)2 (6) was obtained. The related compound [RuCl{κ2(P,O)-i-Pr2PCH2CH2OMe}2(C=CHC6H4-m-CH=C)RuCl{κ2(P,O)-i-Pr2PCH2CH2OMe}2](CF3SO3)2 (7) was prepared from 1, 0.5 equiv of C6H4(CºCH)2-m (5), and silver triflate. The reaction of 2 or 3 with [RhCl(P-i-Pr3)2]2 (8) in the molar ratio of 2:1 yields, by addition of the 14-electron fragment [RhCl(P-i-Pr3)2] to the uncoordinated C—C triple bond, the heterobinuclear complexes [RuCl{κ2(P,O)-i-Pr2PCH2CH2OMe}2(C=CHC6H4-m/p-CºCH)RhCl(P-i-Pr3)2](CF3SO3) (9, 10) which slowly rearrange at room temperature to give the bis(vinylidene) isomers [RuCl{κ2(P,O)-i-Pr2PCH2CH2OMe}2(C=CHC6H4-m/p-CH=C)RhCl(P-i-Pr3)2](CF3SO3) (11, 12).Key words: ruthenium, rhodium, vinylidene complexes, alkyne complexes, phosphine complexes.

2021 ◽  
Vol 99 (2) ◽  
pp. 268-276
Author(s):  
Sunny Kai San Tse ◽  
Herman Ho-Yung Sung ◽  
Ian Duncan Williams ◽  
Guochen Jia

Reactions of Cp*OsCl(PPh3)2 (Cp* = pentamethylcyclopentadienyl) with alkynes and alkynols are described. Treatment of Cp*OsCl(PPh3)2 with phenylacetylene and trimethylsilylacetylene gave the vinylidene complexes Cp*OsCl(=C=CHPh)(PPh3) and Cp*OsCl(=C=CH2)(PPh3), respectively. Treatment of Cp*OsCl(PPh3)2 with the internal alkyne dimethyl acetylenedicarboxylate produced the η2-alkyne complex Cp*OsCl(η2-MeO2C≡CCO2Me)(PPh3). Treatment of Cp*OsCl(PPh3)2 with the propargylic alcohol HC≡CC(OH)Ph2 gave the osmium allenylidene complex Cp*OsCl(=C = C=CPh2)(PPh3). The outcomes of the reactions of Cp*OsCl(PPh3)2 with ω-alkynols HC≡C(CH2)nOH are dependent on the length of the -(CH2)n- linker. The reaction with 3-butyn-1-ol produced the cyclic oxycarbene complex Cp*OsCl{=C(CH2)3O}(PPh3) exclusively. The reactions with 4-pentyn-1-ol produced a mixture of the hydroxyalkyl vinylidene complex Cp*OsCl{=C=CH(CH2)3OH}(PPh3) and the cyclic oxycarbene complex Cp*OsCl{=C(CH2)4O}(PPh3) in about 10:1 molar ratio. The reaction with 5-hexyn-1-ol gave exclusively the hydroxyalkyl vinylidene complex Cp*OsCl{=C=CH(CH2)4OH}(PPh3).


2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Michika Sawada ◽  
Kandi Sridhar ◽  
Yasuharu Kanda ◽  
Shinya Yamanaka

AbstractWe report a synthesis strategy for pure hydroxyapatite (HAp) using an amorphous calcium carbonate (ACC) colloid as the starting source. Room-temperature phosphorylation and subsequent calcination produce pure HAp via intermediate amorphous calcium phosphate (ACP). The pre-calcined sample undergoes a competitive transformation from ACC to ACP and crystalline calcium carbonate. The water content, ACC concentration, Ca/P molar ratio, and pH during the phosphorylation reaction play crucial roles in the final phase of the crystalline phosphate compound. Pure HAp is formed after ACP is transformed from ACC at a low concentration (1 wt%) of ACC colloid (1.71 < Ca/P < 1.88), whereas Ca/P = 1.51 leads to pure β-tricalcium phosphate. The ACP phases are precursors for calcium phosphate compounds and may determine the final crystalline phase.


1982 ◽  
Vol 62 (3) ◽  
pp. 751-757 ◽  
Author(s):  
J. A. BASARAB ◽  
R. T. BERG ◽  
J. R. THOMPSON

The in vitro glucose consumption and lactic acid production by erythrocytes from 20 cattle of a Beef Synthetic (SY) breed group and 25 cattle of a double-muscled (DM) breed group were determined. There were three age groups and two sexes within each breed group. Animals within the DM breed group were categorized as either phenotypically normal- to moderate-muscled (DM carriers) or extreme-muscled (extreme DM) based on the phenotypic expression of the double-muscling trait and on their breeding history. Both DM phenotypes had higher (P < 0.01) erythrocyte glucose consumption and lactic acid production than normal-muscled, noncarrier cattle of the SY breed group. Extreme DM cattle were not different (P > 0.05) in either their erythrocyte glucose consumption or lactic acid production compared with DM carriers. No difference (P > 0.05) due to breed or phenotype was observed in the molar ratio of lactic acid produced to glucose consumed by erythrocytes. These results suggest that carriers of the Double Muscled Syndrome, regardless of phenotypic expression of the double-muscling trait, have a higher rate of erythrocyte glycolysis than normal cattle. Key words: Cattle, double muscled, erythrocyte, glucose, lactic acid


2015 ◽  
Vol 71 (11) ◽  
pp. 1384-1387
Author(s):  
Marwen Chouri ◽  
Habib Boughzala

The title compound bis(1,4-diazoniabicyclo[2.2.2]octane) di-μ-chlorido-bis[tetrachloridobismuthate(III)] dihydrate, (C6H14N2)2[Bi2Cl10]·2H2O, was obtained by slow evaporation at room temperature of a hydrochloric aqueous solution (pH = 1) containing bismuth(III) nitrate and 1,4-diazabicyclo[2.2.2]octane (DABCO) in a 1:2 molar ratio. The structure displays a two-dimensional arrangement parallel to (100) of isolated [Bi2Cl10]4−bioctahedra (site symmetry -1) separated by layers of organic 1,4-diazoniabicyclo[2.2.2]octane dications [(DABCOH2)2+] and water molecules. O—H...Cl, N—H...O and N—H...Cl hydrogen bonds lead to additional cohesion of the structure.


2006 ◽  
Vol 84 (10) ◽  
pp. 1268-1272 ◽  
Author(s):  
Aaron W Amick ◽  
Keith S Griswold ◽  
Lawrence T Scott

An efficient gram scale synthesis of the previously unknown 4,7-di-tert-butylacenaphthenone (3b) is reported. The facile isomerization of epoxide 9b to ketone 3b occurs simply on stirring a solution of 9b with silica gel at room temperature. Aldol cyclotrimerization of 3b with titanium tetrachloride gives 2,5,8,11,14,17-hexa-tert-butylde cacyclene (1b) in 58% isolated yield. X-ray crystal structures have been obtained for the synthetic intermediates 4,7-di-tert-butylacenaphthene (2b) and 4,7-di-tert-butylacenaphthylene (8b).Key words: aromatic, decacyclene, hydrocarbon, nonalternant, polycyclic.


2011 ◽  
Vol 50 (44) ◽  
pp. 10414-10416 ◽  
Author(s):  
Ricardo Rodriguez ◽  
David Gau ◽  
Tsuyoshi Kato ◽  
Nathalie Saffon-Merceron ◽  
Abel De Cózar ◽  
...  

2018 ◽  
Vol 73 (9) ◽  
pp. 641-645 ◽  
Author(s):  
Sepehr Sadegh-Samiei ◽  
Shahrzad Abdolmohammadi

AbstractA novel and efficient synthesis of eight 5-aryl-1,3-dimethyl-2,4-dioxo-1,2,3,4,5,8-hexahydropyrido[2,3-d]pyrimidine-7-carboxylic acids using a TiO2/SiO2 nanocomposite with a molar ratio of 1:1 as a recyclable heterogeneous catalyst is described. The desired products, five of which are new, are formed in short reaction times (2–3 h) with high to excellent yields (94%–98%) under very moderate reaction conditions (room temperature, aqueous media).


Minerals ◽  
2018 ◽  
Vol 8 (12) ◽  
pp. 565 ◽  
Author(s):  
Norman Toro ◽  
Nelson Herrera ◽  
Jonathan Castillo ◽  
Cynthia Torres ◽  
Rossana Sepúlveda

In this study, the surface optimization methodology was used to assess the effect of three independent variables—time, particle size and sulfuric acid concentration—on Mn extraction from marine nodules during leaching with H2SO4 in the presence of foundry slag. The effect of the MnO2/Fe ratio and particle size (MnO2) was also investigated. The maximum Mn extraction rate was obtained when a MnO2 to Fe molar ratio of 0.5, 1 M of H2SO4, −320 + 400 Tyler mesh (−47 + 38 μm) nodule particle size and a leaching time of 30 min were used.


1990 ◽  
Vol 45 (10) ◽  
pp. 1416-1424 ◽  
Author(s):  
W. Preetz ◽  
P. Hollmann ◽  
G. Thiele ◽  
H. Hillebrecht

The triply bonded octahalogenodiosmate(III) anions [Os2X8]2-, previously known with X = Cl, Br, have now been extended to include the iodide with two staggered OsI4 units. This compound was prepared by treating [Os2Cl8]2- with Nal at room temperature in acetone solution. The structure determination by X-ray diffractometry on single crystals of (PPN)2[Os2I8] · 2 CH2Cl2, reveals crystallization in the monoclinic system, space group P21/c with Z = 4. The Os-Os triple bond is with 2.212(1) Å the longest within the three octahalogenodiosmates(III). The Raman spectra show ν(OsOs) at 285, [Os2Cl8]2-; at 287, [Os2Br8]2- and for the iodo compound at 270.1 cm-1 with up to three overtones. The spectroscopic constants are calculated to be ω1 = 270.9 cm-1; X11 = -0.50 cm-1. The 10 Κ UV-VIS spectra of solid [(n-C4H9)4N]2[Os2X8] exhibit δ-π* transitions with maxima at 723, 690 and 643 nm, superimposed by vibrational fine structures with long progressions of 195, 211 and 183 cm-1 for X = Cl, Br, I, respectively. Oxidation of [Os2X8]2-, X = Cl, Br with the corresponding halogen leads to the cleavage of the Os-Os bond, and the dekahalogenodiosmates(IV), [Os2X10]2-, are formed


2019 ◽  
Vol 31 (8) ◽  
pp. 1819-1824
Author(s):  
Shivangi Sharma ◽  
Renu Sachar ◽  
G.D. Bajju ◽  
Vikas Sharma

A series of adducts of p-ethylphenyldithiocarbonates of copper(II) [(p-C2H5C6H4OCS2)2Cu] with ethyl pyridines and chloro pyridines have been synthesized in 1:2 molar ratio. They were characterized by elemental analysis, magnetic susceptibility and molar conductance measurements, infrared, electronic, electron spin resonance and mass spectroscopy, NMR and thermogravimetric analysis. In addition, antifungal studies of these adducts were also performed. The results revealed that the adducts have 1:2 stoichiometry, non-electrolytic and paramagnetic at room temperature. On the basis of spectral studies, a distorted octahedral geometry is proposed around copper(II) ion. ESR studies depicted elongated axial symmetry of Cu(II)adducts with nitrogen donors. Moreover, the adducts also showed potential antifungal activity against Fusarium oxysporium.


Sign in / Sign up

Export Citation Format

Share Document