Platinum(II) phosphine and orotate complexes with aminopyridine co-ligands, and their molecular recognition via hydrogen bonding

The new complexes [Pt(dppp)(py)(2)][OTf](2), 1, [Pt(dppp)(2-ap)(2)][OTf](2), 2, [(dppp)Pt(mu -OH){mu -NH(C5H3N)NH2}Pt(dppp)][OTf](2), 3 (py=pyridine, 2-ap=2-aminopyridine, NH(C5H3N)NH2=2,6-diaminopyridine anion, dppp = 1,3-bis(diphenylphosphino)propane, OTf=O3SCF3) have been prepared via reactions between [Pt(dppp)(OTf)(2)] and pyridine, 2-aminopyridine or 2,6-diaminopyridine (2,6-dap) respectively. The amines exhibit a range of co-ordination modes. Pyridine and 2-aminopyridine co-ordinate to platinum through endo-nitrogen atoms in complexes 1 and 2, the latter existing as a pair of rotomers due to the steric hindrance introduced by the 2-substituent. However, 2,6-diaminopyridine co-ordinates to platinum through the exo-nitrogen of one amino group, to give the unusual mu -amido complex 3. Reaction of the known orotate chelate complex [Pt(PEt3)(2)(N,O-HL)] [HL=orotate, the dianion of 2,6-dioxo-1,2,3,6-tetrahydropyrimidine-4-carboxylic acid (orotic acid)] with 2,6-dap gave [Pt(PEt3)(2)(2,6-dap)(N-HL)] 4, which contains an unconventional monodentate orotate ligand. In this co-ordination mode the orotate retains an ADA hydrogen bonding site and was found to co-crystallise with 2,6-dap via complementary ADA:DAD triple hydrogen bonds to give [Pt(PEt3)(2)(N-HL)(2,6-dap)].2,6-dap, 5. Complex 5 exhibits a helical chain structure of associated [1+1] adducts in the solid state.

Effect of weak hydrogen bonding and included solvent on the crystal structure of the square-planar complex trans-Pt{PPh2(C16H15)}(2)Cl-2

Crystallisation of the square-planar complex trans-Pt{PPh2(C16H15)}(2)Cl-2 from dichloromethane-diethyl ether (1:1) affords two different solvates; trans-Pt{PPh2(C16H15)}(2)Cl-2. CH2Cl2 1 and trans-Pt{PPh2(C16H15)}(2)Cl-2. Et2O 2; the CH2Cl2 forms H-bonding interactions with the complex whereas the Et2O participates only in weak van der Waals interactions; these differences arise from the different hydrogen-bonding characteristics of each solvent.

Orotate complexes of rhodium(I) and iridium(I): effect of coligand, counter ion, and solvent of crystallisation on association via complementary hydrogen bonding

The new complexes [NEt3H][M(HL)(cod)] (M = Rh 1 or Ir 2; H3L = 2,6-dioxo-1,2,3,6-tetrahydropyrimidine-4-carboxylic acid, erotic acid; cod = cycloocta-1,5-diene) have been prepared by the reaction between [M2Cl2(cod)(2)] and erotic acid in dichloromethane in the presence of Ag2O and NEt3. They crystallise as dichloromethane adducts 1 . CH2Cl2 and 2 . CH2Cl2 from dichloromethane-hexane solutions. These isomorphous structures contain doubly hydrogen-bonded dimers, with additional hydrogen bonding to NEt3H+ cations and bridging CH2Cl2 molecules to form tapes. The use of (NBu4OH)-O-n instead of NEt3 gave the related complex [NBu4n][Rh(HL)(cod)] 1' which has an innocent cation not capable of forming strong hydrogen bonds and in contrast to 1 exists as discrete doubly hydrogen-bonded dimers. Complex 1' cocrystallises with 2,6-diaminopyridine (dap) via complementary triple hydrogen bonds to give [NBu4n][Rh(HL)(cod)]. dap . CH2Cl2 3. Complex 3 exhibits an extended sheet structure of associated [2 + 2] units, with layers of NBu4n, cations separating the sheets. These structural data together with those reported previously for platinum orotate complexes suggest that the steric requirements of the other ligands co-ordinated to the metal are important in influencing their hydrogen-bonding abilities. The solvent of crystallisation, the hydrogen-bonding propensity of the coligand and the nature of the counter ion also determine the type of association in the solid state.

Organometallic polymers: An infinite organoplatinum chain in the solid state formed by (C CH center dot center dot center dot ClPt)hydrogen bonds

The new platinum complex [PtCl[C6H2(CH(2)NMe(2))(2) -2,6-(C=CH)-4)] exhibits a polymeric linear -C=CH ... ClPt-hydrogen-bonded structure in the solid state.

Volumetric properties, viscosity and refractive index of the protic ionic liquid, pyrrolidinium octanoate, in molecular solvents

Densities ([rho]) and viscosities ([eta]) of binary mixtures containing the Protic Ionic Liquid (PIL), pyrrolidinium octanoate with five molecular solvents: water, methanol, ethanol, n-butanol, and acetonitrile are determined at the atmospheric pressure as a function of the temperature and within the whole composition range. The refractive index of all mixtures (nD) is measured at 298.15†K. The excess molar volumes VE and deviation from additivity rules of viscosities [eta]E and refractive index [Delta][phi]n, of pyrrolidinium octanoate solutions were then deduced from the experimental results as well as apparent molar volumes V[phi]i, partial molar volumes and thermal expansion coefficients [alpha]p. The excess molar volumes VE are negative over the entire mole fraction range for mixture with water, acetonitrile, and methanol indicating strong hydrogen-bonding interaction for the entire mole fraction. In the case of longest carbon chain alcohols (such as ethanol and n-butanol)†+†pyrrolidinium octanoate solutions, the VE variation as a function of the composition describes an S shape. The deviation from additivity rules of viscosities is negative over the entire composition range for the acetonitrile, methanol, ethanol, and butanol, and becomes less negative with increasing temperature. Whereas, [eta]E of the {[Pyrr][C7CO2]†+†water} binary mixtures is positive in the whole mole fraction range and decreases with increasing temperature. the excess Gibbs free energies of activation of viscous flow ([Delta]G*E) for these systems were calculated. The deviation from additivity rules of refractive index [Delta][phi]n are positive over the whole composition range and approach a maximum of 0.25 in PIL mole fraction for all systems. The magnitude of deviation for [Delta][phi]n describes the following order: water†>†methanol†>†acetonitrile†>†ethanol. Results have been discussed in terms of molecular interactions and molecular structures in these binary mixtures.

Organometallic hydrogen transfer and dehydrogenation catalysts for the conversion of bio-renewable alcohols

Organometallic hydrogen transfer and dehydrogenation provide straightforward atom efficient routes from alcohols to a variety of chemical products. The potential of these reactions to enable the conversion of biomass to value added chemicals is discussed, with reference to the products that can be prepared from aliphatic alcohols in good isolated yield.

Amination and dehydration of 1,3-propanediol by hydrogen transfer: reactions of a bio-renewable platform chemical

1,3-propanediol was subjected to a range of amination conditions. The N-heterocyclic carbene piano stool complex [Cp*IrCl2(bmim)] was found to be a good catalyst for amination and dehydration in toluene or ionic liquid; product compositions could be tuned by altering the ratio of diol to amine.

Preferential CO oxidation over a copper-cerium oxide catalyst in a microchannel reactor

The activity of a 5-wt% Cu/CeO2-x catalyst during preferential CO oxidation in hydrogen-rich gas mixtures was studied in a microchannel reactor. The CO concentration dropped from 1 vol.% to 10 ppm at a selectivity of 60%, at a temperature of 190 degrees C, and a weight hour space velocity (WHSV) of 55,000 cm(3) g(-1) h(-1). Both the CO concentration and the temperature increased when the WHSV was increased from 50,000 to 500,000 cm(3) g(-1) h(-1). An increase of the O-2 concentration from a 1.2 to 3 fold excess reduced the CO concentration to 10 ppm in a broad temperature interval of 50 degrees C at WHSVs up to 275,000 cm(3) g(-1) h(-1). The preferential CO oxidation could be carried out at higher flow rates and at higher selectivities in the microchannel reactor compared to a fixed-bed flow reactor. (C) 2008 Elsevier B.V. All rights reserved.

Photocatalytic evolution of hydrogen and oxygen from ceramic wafers of commercial titanias

Several commercial titania photocatalyst powders were formed into thin (ca. 350 mu m), 25 mm diameter ceramic wafers, sputter deposited with Pt on one side. The activities of each of the ceramic wafers were tested for hydrogen and oxygen evolution from aqueous sacrificial systems. The commercial sample PC50 (Millennium Chemicals, UK) yielded reproducible ceramic wafers with high activity for water photoreduction. Many of the ceramic wafers displayed low water photo-oxidation activities; however, these were greatly increased with addition of a NiO co-catalyst. In a selected case, hydrogen evolution activity was compared between a PC50 wafer and an identical weight of platinised PC50 powder suspension. (C) 2010 Elsevier B.V. All rights reserved.

Hydrogen peroxide vapour indicator

A hydrogen peroxide vapour indicator is described comprising a triarylmethane dye, lissamine green (LG), dissolved in a polymer, polyvinyl alcohol (PVA). The indicator is green/blue in the absence of hydrogen peroxide vapour but is rapidly bleached in the presence of hydrogen peroxide vapour. The kinetics of LG bleaching appear approximately first order with respect [LG] and the concentration of H2O2, which, in turn, is proportional to the partial pressure of H2O2. However, the kinetics also appear to depend directly upon the reciprocal of the film thickness, implying some dependence upon the diffusion of the H2O2 vapour through the indicator film. Like most other H2O2 indicator films (such as starch-iodide paper), the LG/PVA indicator is not particularly selective and responds to most other volatile strong oxidising agents, such as ozone and chlorine. However, it is rapid in response (