Trichloride Trihydrate Research Articles

Synthesis and Characterization of Ru(III) Complexes Containing Quinazoline Derivatives and their Biological and Catalytic Activities

Ruthenium trichloride trihydrate (RuCl3·3H2O) reacted with quinazoline derivative ligands (L) in 1:1 mole ratio in acetone to yield a series of brown/green/greenish black ruthenium(III) complexes of the type RuX3L·nH2O where X = Cl, n = 0, 1, 2 and 3 and L is 6-R-5,6-dihydrobenzoimidazo[1,2- c]quinazoline (R = ethyl: L1/n or i-propyl: L2, L3/n or i-butyl: L4, L5/phenyl: L6/furyl: L7/thiophenyl: L8/o or p-hydroxyphenyl: L9, L10/o or p-chlorophenyl: L11, L12/dimethylaminophenyl: L13). All the synthesized Ru(III) complexes were characterized by elemental analyses, conductivity measurements, infrared, electronic, ESR and mass spectral techniques, TGA, magnetic susceptibility and electrochemical studies. A square pyramidal geometry around the metal ion was proposed for all the complexes. The biological activities of the ligand and its ruthenium(III) complexes have been studied on microorganisms such as B. subtilis, E. coli and yeast by cup-plate method. The catalytic activity of the synthesized ruthenium(III) complexes towards oxidation of benzyl alcohol, cyclohexanol and hydroquinone was also carried out in acetonitrile with tert.-butyl hydroperoxide (t-BuOOH) as co-oxidant.

Rhodium(III) and Platinum(II) Complexes of Azamacrocycle: Synthesis, Characterization and Antimicrobial Evaluation

A dihydroperchlorate salt of octamethyl derivative of 14-membered tetraazamacrocycle, Me8[14]diene·2HClO4 (L·2HClO4), was formed by the condensation of 1,2-diamino propane with acetone in the presence of a quantitative amount of perchloric acid, which on extraction with chloroform at pH above 12 yielded free ligand (L). The interaction of rhodium(III) trichloride trihydrate and platinum(II) chloride with free ligand L produced six-coordinated octahedral orange-red complex, cis-[RhLCl2]Cl and four-coordinated square-planar yellow complex, [PtL]Cl2, respectively. Axial substitution reactions on [RhLCl2]Cl with KX (X = NO3, Br or I) and NaNO2 afforded six-coordinated deep brown products [RhLY2]Y (Y= NO3, Br, I or NO2). The ligand and metal complexes were characterized based on analytical, molar conductivity, spectroscopic and magnetochemical data. The antimicrobial activities of the concerned ligand and its complexes have been explored against some selected bacteria and fungi.

Thermal stability and electrochemical properties of PVP-protected Ru nanoparticles synthesized at room temperature

Stable ruthenium nanoparticles (RuNPs) have been synthesized by the chemical reduction of ruthenium trichloride trihydrate (RuCl3 · 3H2O) using sodium borohydride (NaBH4) as a reductant and polyvinylpyrrolidone (PVP) as a protecting agent in the aqueous medium at room temperature. The nanoparticles thus prepared were characterized by their morphology and structural analysis from transmission electron microscopy (TEM), X-ray powder diffraction (XRD), UV–vis spectroscopy, Fourier transformation infrared and thermogravimetric analysis (TGA) techniques. The TEM image suggested a homogeneous distribution of PVP-protected RuNPs having a small average diameter of 2–4 nm with a chain-like network structure. The XRD pattern also confirmed that a crystallite size is around 2 nm of PVP-protected RuNPs having a single broad peak. The thermal stability studied using TGA, indicated good stability and the electrochemical properties of these nanoparticles revealed that saturation current increases for PVP-protected RuNPs/GC.

Ruthenium(II) bipyridine complexes incorporating (NN′S) azoimine ancillary ligands. Synthesis, spectroscopy, solid state structure and DFT calculations

Four ruthenium complexes of N’NS donor thiomethyl-azoimine ligands (L) of the general type trans-[RuII(bipy)(L)(Cl)2](C1–C4) (L=XC6H4NNC(COMe)NC6H4(2-SMe), X=H (L1), C1; CH3 (L2), C2; Br (L3), C3; NO2 (L4), C4) have been synthesized by the reaction of ruthenium trichloride trihydrate with the corresponding L ligands and bipyridine (bipy) in refluxing ethanol. The molecular structure of trans-[Ru(bpy)(L3)(Cl)2](C3) in the solid state is reported. The thiomethyl-azoimine ligands (L) bind as NN′ bidentate ligands with no direct Ru–S interaction. Furthermore, the complexes have been characterized by spectroscopic data (IR, UV/Vis and 1H NMR) and cyclic voltammetry. The electrochemical parameters (EL(L)) of the azoimine ligands (L1–L4) are reported. The electronic excitations of a representative complex (C3) are interpreted by DFT and TDDFT calculations.

The Hydroxide‐Promoted Catalytic Hydrodefluorination of Fluorocarbons by Ruthenium in Aqueous Media

AbstractA ruthenium complex ligated by the non‐innocent protic ligand 2,6‐imidizoylpyridine (IPI) in aqueous potassium hydroxide media is shown to be a suitable catalyst for the CF bond activation and subsequent hydrodefluorination (and hydrogenolysis) of a model fluorocarbon. Furthermore, the conversion of CF bonds was enhanced upon increasing the concentration of potassium hydroxide [KOH]. A simple, non‐ligated heterogeneous analogue derived from ruthenium(III) trichloride trihydrate dissolved in aqueous potassium hydroxide is shown to be an even more active catalyst, capable of hydrodefluorination of aryl fluorocarbons at room temperature and alkyl fluorocarbons under more forcing conditions.

In situ time-resolved DXAFS study of Rh nanoparticle formation mechanism in ethylene glycol at elevated temperature

A combination of in situ time-resolved DXAFS and ICP-MS techniques reveals that the formation process of Rh nanoparticles (NPs) from rhodium trichloride trihydrate (RhCl(3)·3H(2)O) in ethylene glycol with polyvinylpyrrolidone (PVP) at elevated temperature is a first-order reaction, which indicates that uniform size Rh NPs appear consecutively and these Rh NPs do not aggregate with each other.

A Practical and Effective Ruthenium Trichloride‐Based Protocol for the Regio‐ and Stereoselective Catalytic Hydroamidation of Terminal Alkynes

AbstractA rational catalyst development based on mechanistic and spectroscopic investigations led to the discovery of a new protocol for catalytic hydroamidation reactions that draws on easily available ruthenium trichloride trihydrate (RuCl3⋅3 H2O) as the catalyst precursor instead of the previously employed, expensive bis(2‐methylallyl)(1,5‐cyclooctadiene)ruthenium(II). This practical and easy‐to‐use protocol dramatically improves the synthetic applicability of Ru‐catalyzed hydroamidations. The catalyst, generated in situ from ruthenium(III) chloride hydrate, tri‐n‐butylphosphine, 4‐(dimethylamino)pyridine and potassium carbonate, effectively promotes the addition of secondary amides, lactams and carbamates to terminal alkynes under formation of (E)‐anti‐Markovnikov enamides. The scope of the new protocol is demonstrated by the synthesis of 24 functionalized enamide derivatives, among them valuable intermediates for organic synthesis.

Ruthenium(II) Complexes Containing Bis(2-(diphenylphosphino)phenyl) Ether and Their Catalytic Activity in Hydrogenation Reactions

The half-sandwich complexes [(eta5-C5H5)RuCl(DPEphos)] (1) and [{(eta6-p-cymene)RuCl2}2(mu-DPEphos)] (2) were synthesized by the reaction of bis(2-(diphenylphosphino)phenyl) ether (DPEphos) with a mixture of ruthenium trichloride trihydrate and cyclopentadiene and with [(eta6-p-cymene)RuCl2]2, respectively. Treatment of DPEphos with cis-[RuCl2(dmso)4] afforded fac-[RuCl2(kappa3-P,O,P-DPEphos)(dmso)] (3). The dmso ligand in 3 can be substituted by pyridine, 2,2'-bipyridine, 4,4'-bipyridine, and PPh3 to yield trans,cis-[RuCl2(DPEphos)(C5H5N)2] (4), cis,cis-[RuCl2(DPEphos)(2,2'-bipyridine)] (5), trans,cis-[RuCl2(DPEphos)(mu-4,4'-bipyridine)]n (6), and mer,trans-[RuCl2(kappa3-P,P,O-DPEphos)(PPh3)] (7), respectively. Refluxing [(eta6-p-cymene)RuCl2]2 with DPEphos in moist acetonitrile leads to the elimination of the p-cymene group and the formation of the octahedral complex cis,cis-[RuCl2(DPEphos)(H2O)(CH3CN)] (8). The structures of the complexes 1-5, 7, and 8 are confirmed by X-ray crystallography. The catalytic activity of these complexes for the hydrogenation of styrene is studied.

Thin and Thick RuO2-TiO2Coatings on Titanium Substrates by the Sol-Gel Process

Thin and thick 20 mol% RuO2–80 mol% TiO2 coatings have been obtained through a combination of different preparation parameters, including catalyst and oxide concentrations, using ruthenium trichloride trihydrate and titanium n-butoxide. Acid catalysed solutions produced uniform, crack-free coatings that were too thin for use on electrocatalysis electrodes. On the other hand, base catalysed solutions produced thicker, cracked coatings. Electrodes prepared with base catalysed solutions performed well in electrocatalysis lifetime testing for corrosion stability.

μ-Aqua-pentaaqua[μ-3,6-bis(6-methyl-2-pyridyl)pyridazine]chlorodinickel(II) trichloride trihydrate

The title compound, μ-aqua-1:2κ2O-penta­aqua-1κ2O,2κ3O-μ-3,6-bis(6-methyl-2-pyridyl)­pyridazine-1κ2N1,N6:2κ2N2,N3-chloro-1κCl-dinickel(II) trichloride trihydrate, [Ni2Cl(C16H14­N4)(H2O)6]Cl3·3H2O, consists of two NiII atoms, a 3,6-bis(6-methyl-2-pyridyl)­pyridazine mol­ecule, four Cl atoms and nine water mol­ecules. The two Ni atoms are octahedrally coordinated by N and Cl atoms, and by water mol­ecules, and the three six-membered rings, a pyridazine and two picolines, are planar to within 0.181 (3) A. The crystal structure is stabilized by an intra- and intermolecular hydrogen-bonding scheme involving water–water and water–chlorine interactions.

ChemInform Abstract: Structure of the Hexagonal Modification of Lanthanum(III) Trichloride Trihydrate.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Transannular cyclisation as a stratagem in synthesis. A total synthesis of (±)-pentalenene

A total synthesis of the triquinane sesquiterpene (±)-pentalenene(1) found in Streptomyces , based on transannular cyclisation of the bicyclo [6.3.0] undecadiene (7) in the presence of boron trifluoride etherate is described. The bicyclo(6.3.0]undecadiene(7) was elaborated from the silyl enol ether(36) using a unique intramolecular [2+2] photocycloaddition - Grob fragmentation sequence leading to (8) [ viz (36)→(37) and (38)→(8)], followed by olefination to (40) and isomerisation in the presence of rhodium trichloride trihydrate.

Regioselective deuterium labelling of aromatic acids, amides and amines using group VIII metal catalysts

AbstractOrtho‐deuterated arylcarboxylic acids and their sodium salts may be prepared with high regioselectivity by isotopic exchange with deuterium oxide in the presence of a range of commercially available group VIII metal complexes. When rhodium trichloride trihydrate is employed a range of arylcarboxamides and arylmethanamines are also selectively labelled at the ortho‐positions.

Trichlorobis(tri-p-tolylarsine)(methanol)ruthenium(III) and some of its reactions with nitrogen donor ligands

The interaction of tri-p-tolylarsine with ruthenium trichloride trihydrate in acidified methanol under reflux gave a complex, RuCl 3(AsTol P 3) 2(MeOH) ( 1). Complex 1 has been employed as a useful starting material for the preparation of other ruthenium(II) and (III) complexes. On treating complex 1 with excess of nitriles, complexes of the type RuCl 3(AsTol P 3) 2(RCN) (R = CH 3, C 6H 5, C 6H 5CH 2) were obtained. Complex 1 gave RuCl 3(AsTol P 3(Py) 2 and RuCl 2(Py) 4 respectively, on reaction with excess of pyridine in n-hexane and dichloromethane. The reactions of 2,2′-bipyridine and 1,10-phenanthroline (NN) with complex 1 in dichloromethane resulted in the formation of RuCl 3(AsTol P 3)(NN). A five coordinate complex RuCl 3(AsTol P 3) 2 was isolated from dichloromethane, chloroform or benzene solutions of complex 1. The dissolution of complex 1 in acetone gave a stable adduct RuCl 3(AsTol P 3) 2(Me 2CO).

Isomerisation of ω-alkenyl substituted cyclohexane-1,3-dione enol derivatives using rhodium catalysis. A practical synthesis of substituted resorcinols

Treatment of the ω-alkenyl substituted cyclohexane-1,3-dione enol derivatives (1), (11), and (13) with rhodium trichloride trihydrate leads to the corresponding resorcinol derivatives (2), (12), and (15) respectively. By contrast, the RhCl 3.3H 2O catalysed isomerisations of the related enol ethers (5) and (9) instead produce the dienones (6) and (10) respectively.

A polymer-supported dichloro(cyclopentadienyl)rhodium(III) catalyst

Insoluble dichloro(η5-cyclopentadienyl)rhodium(II) has been attached to 20% divinylbenzene cross-linked polystyrene by treating polymer-attached cyclopentadiene directly with rhodium trichloride trihydrate. Polymer-supported dichloro (η5 -cyclopentadienyl)rhodium(III), I, is a good hydrogenation catalyst for olefins as well as arenes in the presence of excess triethylamine under 110 psig H2 at 70°C. It can also catalyze isomerization of allylbenzene in the absence of triethylamine at 85°C. Under 80 psig of CO and H2 (1/1) in the presence of triethylamine, I can be easily converted into the polymer-supported η5-cyclopentadienylrhodium dicarbonyl catalyst. Mechanisms for the catalyst preparation, hydrogenation and isomerization are also discussed.

Rhodium-catalysed isomerisation of some unsaturated organic substrates

The versatile rhodium trichloride trihydrate has been employed in catalytic amounts to promote double-bond migration. This method allows good yields in otherwise difficult, or impossible, exocyclic–endocyclic isomeris-ations. The rearrangement of ergosterol was found to be more complex. Besides known isomers a new cis-AB-ergosterol isomer has been isolated.

Products formed from rhodium trichloride trihydrate and allyl alcohol or diallyl ether; the crystal and molecular structure of [Rh2Cl4(C6H11O)2],CH3OH

The structure of the complex [Rh2Cl4(C6H11O)2],CH3OH formed from RhCl3,3H2O and allyl Alcohol is reported as well as a very efficient rhodium-catalysed cyclisation of diallyl ether.

Some complexes of rhodium(I), rhodium(II), and rhodium(III) containing tertiary t-butylphosphines as ligands

Paramagnetic rhodium(II) complexes of the type trans-[RhCl2(PBut2R)2](R = Me, Et, or Prn) are formed rapidly by treating ethanolic rhodium(III) chloride trihydrate with the tertiary phosphine at 25 °C. The complexes have low magnetic moments in the solid state (<1·4 B.M.) but in solution trans-[RhCl2(PBut2Me)2] has the expected moment of ca. 2·12 B.M. Treatment of rhodium trichloride trihydrate with some t-butylphosphines (L = PButPrn2, PBut2Me, PBut2Et, or PBut2Prn) in refluxing propan-2-ol gives square pyramidal hydridorhodium(III) complexes [RhHCl2L2]. [RhHCl2(PButPrn2)2] reacts with some ligands Q [Q = MeNC, MeCN, pyridine, or P(OMe)3] to give complexes of type [RhHCl2(PButPrn2)2Q]. [RhHCl2(PBut2Me)2] reacts with hydrogen gas to give [RhH2Cl(PBut2Me)2], and trans-[RhCl2(PBut2Me)2] with hydrogen gas gives a ca. 1 : 1 mixture of [RhHCl2(PBut2Me)2] and [Rh2Cl(PBut2Me)2]. Treatment of rhodium chloride in propan-2-ol with tri-t-butylphosphine gives the five-co-ordinate dihydride [RhH2Cl(PBut3)2]. [RhH2Cl(PButMePh)3] was formed similarly as a mixture of enantiomers. Prolonged (7 days) treatment of hydrated rhodium trichloride in ethanol at 20 °C with di-t-butylalkylphosphines gives rhodium(I) carbonyl complexes trans-[RhCl(CO)(PBut2R)2](R = Me, Et, or Prn) in ca. 75% yield. Addition of a strong base (e.g., NaOMe) to solutions of complexes of the type [RhHCl2L2] in ethanol or methanol gives trans-[RhCl(CO)L2] within a few seconds. Ethanolic rhodium trichloride reacts with PHBut2 to give [RhCl(PHBut2)3]. 1H and 31P N.m.r., i.r., and electronic absorption spectral data are reported and discussed as are magnetic susceptibility data for the rhodium(II) complexes.

Products formed from 2-methylallyl alcohol and rhodium trichloride trihydrate. Determination of the structure of [RhCl2(C8H15O)(4-methylpyridine)2]2 by X-ray crystallography

Rhodium trichloride trihydrate and 2-methyl-allyl alcohol react to give [RhCl2(C8H15O2)]n which with 4-methylpyridine gives [RhCl2(C8H15O2)(4-methylpyridine)2]2, the structure of which has been determined by X-ray diffraction.