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Synthesis of a Benzodiazepine-derived Rhodium NHC Complex by C-H Bond Activation

Description: The synthesis and characterization of a Rh(I)-NHC complex generated by C-H activation of 1,4-benzodiazepine heterocycle are reported. This complex constitutes a rare example of a carbene tautomer of a 1,4-benzodiazepine aldimine stabilized by transition metal coordination and demonstrates the ability of the catalytically relevant RhCl(PCy{sub 3}){sub 2} fragment to induce NHC-forming tautomerization of heterocycles possessing a single carbene-stabilizing heteroatom. Implications for the synthesis of benzodiazepines and related pharmacophores via C-H functionalization are discussed.
Date: January 30, 2008
Creator: Bergman, Roberg G.; Gribble, Jr., Michael W. & Ellman, Jonathan A.
Partner: UNT Libraries Government Documents Department

Optimization of Rhodium-Based Catalysts for Mixed Alcohol Synthesis -- 2010 Progress Report

Description: Pacific Northwest National Laboratory has been conducting research for the U.S. Department of Energy, Energy Efficiency Renewable Energy, Biomass Program to investigate the feasibility of producing mixed alcohols from biomass-derived synthesis gas. In recent years this research has primarily involved the further development of a silica-supported catalyst containing rhodium and manganese that was selected from earlier catalyst screening tests. A major effort during 2010 was to examine alternative catalyst supports to determine whether other supports, besides the Davisil 645 silica, would improve performance. Optimization of the Davisil 645 silica-supported catalyst also was continued with respect to candidate promoters iridium, platinum, and gallium, and examination of selected catalyst preparation and activation alternatives for the baseline RhMn/SiO2 catalyst.
Date: October 1, 2010
Creator: Gerber, Mark A.; Gray, Michel J.; Albrecht, Karl O.; White, J. F.; Rummel, Becky L. & Stevens, Don J.
Partner: UNT Libraries Government Documents Department

Optimization of Rhodium-Based Catalysts for Mixed Alcohol Synthesis -- 2011 Progress Report

Description: Pacific Northwest National Laboratory has been conducting research to investigate the feasibility of producing mixed alcohols from biomass-derived synthesis gas (syngas). In recent years, this research has primarily involved the further development of catalysts containing rhodium and manganese based on the results of earlier catalyst screening tests. Research during FY 2011 continued to examine the performance of RhMn catalysts on alternative supports including selected zeolite, silica, and carbon supports. Catalyst optimization continued using both the Davisil 645 and Merck Grade 7734 silica supports. Research also was initiated in FY 2011, using the both Davisil 645 silica and Hyperion CS-02C-063 carbon supports, to evaluate the potential for further improving catalyst performance, through the addition of one or two additional metals as promoters to the catalysts containing Rh, Mn, and Ir.
Date: October 1, 2011
Creator: Gerber, Mark A.; Gray, Michel J.; Albrecht, Karl O. & Rummel, Becky L.
Partner: UNT Libraries Government Documents Department

Rhodium Nanoparticle Shape Dependence in the Reduction of NO by CO

Description: The shape dependence of the catalytic reduction of NO by CO on Rhodium nanopolyhedra and nanocubes was studied from 230-270 C. The nanocubes are found to exhibit higher turnover frequency and lower activation energy than the nanopolyhedra. These trends are compared to previous studies on Rh single crystals.
Date: July 13, 2009
Creator: Renzas, J.R.; Zhang, Y.; Huang, W. & Somorjai, G.A.
Partner: UNT Libraries Government Documents Department

Evidence for CO Dissociation on Rhodium Surfaces

Description: Carbon monoxide adsorbs molecularly on rhodium surfaces at 300K, but if the rhodium samples are heated in the presence of carbon monoxide, there is evidence for carbon-oxygen bond breaking at step and/or defect sites. The effects of step and defect site density, subsurface oxygen concentration, and oxygen dissolution into the rhodium lattice on CO dissociation are discussed.
Date: June 1, 1980
Creator: Castner, D. G.; Dubois, L. H.; Sexton, B. A. & Somorjai, G. A.
Partner: UNT Libraries Government Documents Department

Optimization of Rhodium-Based Catalysts for Mixed Alcohol Synthesis -- 2009 Progress Report

Description: Pacific Northwest National Laboratory (PNNL) has been conducting research for the United States Department of Energy, Energy Efficiency Renewable Energy, Biomass Program to investigate the feasibility of producing mixed alcohols from biomass-derived synthesis gas (syngas). This research has involved the screening of potential catalysts, and optimization of the more promising ones, using laboratory scale reactors. During 2009, the main goal of the testing program focused on optimizing selected supported catalysts containing rhodium (Rh) and manganese (Mn). Optimization involved examining different total concentrations and atomic ratios of Rh and Mn as well as that of the more promising promoters (Ir and Li) identified in the earlier screening studies. Evaluation of catalyst performance focused on attaining improvements with respect to the space-time-yield and converted carbon selectivity to C2+ oxygenates, with additional consideration given to the fraction of the oxygenates that were C2+ alcohols.
Date: December 21, 2010
Creator: Gerber, Mark A.; Gray, Michel J.; Stevens, Don J.; White, J. F. & Rummel, Becky L.
Partner: UNT Libraries Government Documents Department

Design of a high activity and selectivity alcohol catalyst. Ninth quarterly report, August 7, 1992--November 7, 1992

Description: Efforts to synthesize bimetallic cluster-derived Rh-Mo catalysts for CO and CO{sub 2} hydrogenation to preferentially produce oxygenates. The rhodium-molybdenum cluster, (PPh{sub 3}){sub 2}RhMO(CO)({mu}-CO){sub 2}Cp, was employed as a precursor to alumina- and silica-supported catalysts which were in CO hydrogenation. When compared to catalysts made from the distinct organometallic complexes, RhH(CO)(PPh{sub 3}){sub 3} and [MO(CO){sub 3}Cp]{sub 2}, the catalysts derived from a binuclear precursor show higher activities for CO hydrogenation and superior selectivities towards oxygenates, namely, methanol, dimethyl ether and ethanol. Their product distributions depend on the support. Fourier transform infrared spectroscopy studies indicate that CO chemisorbs on cluster-derived catalysts as gem-dicarbonyls while it is chemisorbed only in the linear-carbonyl configuration on catalysts made from separate rhodium and molybdenum complexes. The particular oxygenate selectivity of the cluster-derived catalysts may be correlated to the strong electronic interaction between Rh and Mo. Carbon dioxide hydrogenation has also been carried out on the catalysts mentioned above. Again, the cluster-derived catalysts show higher oxygenate selectivities. Finally, the catalysts were studied with regard to both CO and CO{sub 2} hydrogenation kinetics, apparent activation energies inferred.
Date: November 30, 1992
Creator: Foley, H. C. & Mills, G. A.
Partner: UNT Libraries Government Documents Department

Seedless Polyol Synthesis and CO Oxidation Activity of Monodisperse (111) and (100)-Oriented Rhodium Nanocrystals in Sub-10 nm Sizes

Description: Monodisperse sub-10 nm (6.5 nm) sized Rh nanocrystals with (111) and (100) surface structures were synthesized by a seedless polyol reduction in ethylene glycol, with poly(vinylpyrrolidone) as a capping ligand. When using [Rh(Ac){sub 2}]{sub 2} as the metal precursor, (111)-oriented Rh nanopolyhedra containing 76% (111)-twined hexagons (in 2D projection) were obtained; whereas, when employing RhCl{sub 3} as the metal precursor in the presence of alkylammonium bromide, such as tetramethylammonium bromide and trimethyl(tetradecyl)ammonium bromide, (100)-oriented Rh nanocubes were obtained with 85% selectivity. The {l_brace}100{r_brace} faces of the Rh nanocrystals are stabilized by chemically adsorbed Br{sup -} ions from alkylammonium bromides, which led to (100)-oriented nanocubes. Monolayer films of the (111)-oriented Rh nanopolyhedra and (100)-oriented Rh nanocubes were deposited on silicon wafers in a Langmuir-Blodgett trough to make model 2D nanoarray catalysts. These nanocatalysts were active for CO oxidation by O{sub 2}, and the turnover frequency was independent of nanoparticle shape, consistent with that previously observed for Rh(111) and Rh(100) single crystals.
Date: March 15, 2010
Creator: Zhang, Yawen; Grass, Michael E.; Huang, Wenyu & Somorjai, Gabor A.
Partner: UNT Libraries Government Documents Department

Rhodium-Catalyzed C-C Bond Formation via Heteroatom-Directed C-H Bond Activation

Description: Once considered the 'holy grail' of organometallic chemistry, synthetically useful reactions employing C-H bond activation have increasingly been developed and applied to natural product and drug synthesis over the past decade. The ubiquity and relative low cost of hydrocarbons makes C-H bond functionalization an attractive alternative to classical C-C bond forming reactions such as cross-coupling, which require organohalides and organometallic reagents. In addition to providing an atom economical alternative to standard cross - coupling strategies, C-H bond functionalization also reduces the production of toxic by-products, thereby contributing to the growing field of reactions with decreased environmental impact. In the area of C-C bond forming reactions that proceed via a C-H activation mechanism, rhodium catalysts stand out for their functional group tolerance and wide range of synthetic utility. Over the course of the last decade, many Rh-catalyzed methods for heteroatom-directed C-H bond functionalization have been reported and will be the focus of this review. Material appearing in the literature prior to 2001 has been reviewed previously and will only be introduced as background when necessary. The synthesis of complex molecules from relatively simple precursors has long been a goal for many organic chemists. The ability to selectively functionalize a molecule with minimal pre-activation can streamline syntheses and expand the opportunities to explore the utility of complex molecules in areas ranging from the pharmaceutical industry to materials science. Indeed, the issue of selectivity is paramount in the development of all C-H bond functionalization methods. Several groups have developed elegant approaches towards achieving selectivity in molecules that possess many sterically and electronically similar C-H bonds. Many of these approaches are discussed in detail in the accompanying articles in this special issue of Chemical Reviews. One approach that has seen widespread success involves the use of a proximal heteroatom that serves as a directing ...
Date: May 13, 2010
Creator: Colby, Denise; Bergman, Robert & Ellman, Jonathan
Partner: UNT Libraries Government Documents Department

Colloid Science of Metal Nanoparticle Catalysts in 2D and 3D Structures. Challenges of Nucleation, Growth, Composition, Particle Shape, Size Control and their Influence on Activity and Selectivity

Description: Recent breakthroughs in synthesis in nanosciences have achieved control of size and shapes of nanoparticles that are relevant for catalyst design. In this article, we review the advance of synthesis of nanoparticles, fabrication of two and three dimensional model catalyst system, characterization, and studies of activity and selectivity. The ability to synthesize monodispersed platinum and rhodium nanoparticles in the 1-10 nm range permitted us to study the influence of composition, structure, and dynamic properties of monodispersed metal nanoparticle on chemical reactivity and selectivity. We review the importance of size and shape of nanoparticles to determine the reaction selectivity in multi-path reactions. The influence of metal-support interaction has been studied by probing the hot electron flows through the metal-oxide interface in catalytic nanodiodes. Novel designs of nanoparticle catalytic systems are discussed.
Date: February 13, 2008
Creator: Somorjai, Gabor A. & Park, Jeong Y.
Partner: UNT Libraries Government Documents Department


Description: Plant scale tests were conducted to determine the feasibility of decomposing the nitrous oxide in dissolver off gases with a heated rhodium catalyst. The test results from two fixed bed reactors operating on off gases containing between 14.2 and 19.8 vol.% nitrous oxide show that the nitrous oxide content can be reduced to less than 0.05% with catalyst bed outlet at 1300 to 1500 deg F and space velocities at 472 to 700 hr/sup -//sup 1/. Rate constants appear to be comparable to those reported in the literature. Suggestions are made for the design of a permanent installation. (auth)
Date: April 17, 1961
Creator: Lakey, L.T.
Partner: UNT Libraries Government Documents Department

Rh-Based Mixed Alcohol Synthesis Catalysts: Characterization and Computational Report

Description: The U.S. Department of Energy is conducting a program focused on developing a process for the conversion of biomass to bio-based fuels and co-products. Biomass-derived syngas is converted thermochemically within a temperature range of 240 to 330°C and at elevated pressure (e.g., 1200 psig) over a catalyst. Ethanol is the desired reaction product, although other side compounds are produced, including C3 to C5 alcohols; higher (i.e., greater than C1) oxygenates such as methyl acetate, ethyl acetate, acetic acid and acetaldehyde; and higher hydrocarbon gases such as methane, ethane/ethene, propane/propene, etc. Saturated hydrocarbon gases (especially methane) are undesirable because they represent a diminished yield of carbon to the desired ethanol product and represent compounds that must be steam reformed at high energy cost to reproduce CO and H2. Ethanol produced by the thermochemical reaction of syngas could be separated and blended directly with gasoline to produce a liquid transportation fuel. Additionally, higher oxygenates and unsaturated hydrocarbon side products such as olefins also could be further processed to liquid fuels. The goal of the current project is the development of a Rh-based catalyst with high activity and selectivity to C2+ oxygenates. This report chronicles an effort to characterize numerous supports and catalysts to identify particular traits that could be correlated with the most active and/or selective catalysts. Carbon and silica supports and catalysts were analyzed. Generally, analyses provided guidance in the selection of acceptable catalyst supports. For example, supports with high surface areas due to a high number of micropores were generally found to be poor at producing oxygenates, possibly because of mass transfer limitations of the products formed out of the micropores. To probe fundamental aspects of the complicated reaction network of CO with H2, a computational/ theoretical investigation using quantum mechanical and ab initio molecular dynamics calculations was initiated in ...
Date: August 1, 2013
Creator: Albrecht, Karl O.; Glezakou, Vassiliki Alexandra; Rousseau, Roger J.; Engelhard, Mark H.; Varga, Tamas; Colby, Robert J. et al.
Partner: UNT Libraries Government Documents Department

Decomposition of Nitrous Oxide Final Report. Period Covered: February 19, 1959-August 18, 1959

Description: The decomposition of N/sub 2/O in a reactor tube containing various fixed-bed catalysts was investigated at 200 to 700 deg C, space velocities of 250, 1250, and 2500 vol. of gas per vol. of catalyst per hr, and various gas mixture compositions. As catalysts, En at 500 deg C and Pd at 650 deg C both gave satisfactory results. NO/sub 2/ was formed with all these catalysts, the amount increasing as the residual N/sub 2/O decreased. (C.J.G.)
Date: August 31, 1959
Creator: Zufall, J. H. & Miller, H. S.
Partner: UNT Libraries Government Documents Department

Bioorganometallic Chemistry, Part 15. A novel molecular recognition process of host, trans-[Cp*Rh({eta}{sup 1}(N3)-1-methylcytosine)({mu}-OH)]{sub 2} (OTf){sub 2}, with l-aromatic amino acid guests: selective hydrogen bonding to the {mu}-OH groups and the 1-methylcytosine ligands

Description: The {sup 1}H-NMR and computer docking experiments have elucidated a novel molecular recognition process of host, trans-[Cp*Rh({eta}{sup 1}(Ne)-1-methylcytosine)({mu}-OH)]{sub 2}(OTf){sub 2} (1), with L-aromatic amino acids, which is predicated on a selective hydrogen bonding regime of the NH{sub 3}{sup +} of the amino acid to one of the Rh-{mu}-OH groups, as well as to a C{double_bond}O group of one of the other 1-methycytosine ligands, while the COO{sup -} H-bonds to an NH{sub 2} of the other 1-methycytosine ligand.
Date: November 1, 2002
Creator: Elduque, Anabel; Carmona, Daniel; Oro, Luis; Eisenstein, Miriam & Fish, Richard H.
Partner: UNT Libraries Government Documents Department

Fundamental studies of hydrogen chemisorption on supported monometallic and bimetallic catalysts using microcalorimetry

Description: Highly dispersed transition metal catalysts are used in numerous commercial processes such as hydrocarbon conversions. For example, the use of Pt supported on acidic alumina or silica-alumina for reforming of naphtha in the production of gasoline is well known. Another use of supported catalysts is in automobile emission control where supported Pt-Rh bimetallic catalysts are used. Supported Ru can be used in Fischer-Tropsch synthesis for the production of higher hydrocarbons from synthesis gas. While many of these catalyst systems have been in commercial operation for several decades there is still a lack of consensus regarding the exact role of the catalyst on a molecular level. In particular, little is known about the mechanisms operating on the catalyst surface at the high pressure and high temperature conditions typically used in commercial operations. This report contains the general introduction and conclusions and an appendix containing the operating instructions for a microcalorimeter. Three chapters have been processed separately. They are: the effect of K on the kinetics and thermodynamics of hydrogen adsorption on Ru/SiO{sub 2}; hydrogen adsorption states on silica supported Ru-Ag and Ru-Cu bimetallic catalysts investigated via microcalorimetry; a comparative study of hydrogen chemisorption on silica supported Ru, Rh, and Pt.
Date: June 24, 1997
Creator: Narayan, R.L.
Partner: UNT Libraries Government Documents Department

Pressure-composition-isotherms of palladium alloys

Description: About one year ago a summary report was submitted covering the previous three years of the contract. This earlier report should be consulted as a useful survey and evaluation of the research carried out by the authors. Because of difficulties during the current contract period arising from the anomalous nature of the melt-spun alloys received from LANL, it is not possible to contribute much beyond that given in last year's summary with regard to the overall picture of the behavior of Pd-rich alloys towards hydrogen and its isotopes. In this contract year deuterium was employed instead of hydrogen and instead of using cycled alloys, the alloys employed for each isotherm measurement were in their virgin condition. Because of the anomalous behavior of the melt-spun alloys, it was not feasible or worthwhile in some cases, e.g., when the alloy behaved anomalously, to carry out all of the originally proposed work. Nonetheless considering these obstacles, some useful data were obtained. For example, the obtaining of deuterium isotherms for the Pd-Rh alloys down to {minus}40 C using internally oxidized melt-spun alloys may prove to be useful.
Date: November 1, 1996
Creator: Flanagan, T.B.
Partner: UNT Libraries Government Documents Department

Metal-ceramic interfaces: Overlayer-induced reconstruction and magnetism of 4d transition-metal monolayers

Description: Structural, electronic, and magnetic properties of metal-ceramic interfaces, M/MgO(001) (M=Pd, Rh, and Ru), have been investigated using the full potential linearized augmented-plane-wave method. Ru and Rh monolayers are found to be able to retain large spin magnetic moments on MgO(001) (1.95 {mu}{sub B} and 1.21 {mu}{sub B} for Ru and Ph; respectively) -- indicating, in principle, the potential application of MgO(001) as a benign substrate for 4d monolayer magnetism. Significantly, according to our atomic-force determinations, the metal overlayers induce a sizable buckling reconstruction in the interfacial MgO layer, which enhances the M-MgO binding energy by 0.1 eV. The weak M-0 interaction is mainly via tail effects; however, it affects the density of states at the Fermi level for Pd/Mg0(001) significantly and completely eliminates the small magnetic moment of the free Pd monolaver (0.34{mu}{sub B}).
Date: February 15, 1995
Creator: Wu, R. & Freeman, A.J.
Partner: UNT Libraries Government Documents Department

Scanning tunneling microscopy studies of organic monolayers adsorbed on the rhodium(111) crystal surface

Description: Scanning Tunneling Microscopy studies were carried out on ordered overlayers on the (111) surface of rhodium. These adsorbates include carbon monoxide (CO), cyclohexane, cyclohexene, 1,4-cyclohexadiene, para-xylene, and meta-xylene. Coadsorbate systems included: CO with ethylidyne, CO with para- and meta-xylene, and para-xylene with meta-xylene. In the case of CO, the structure of the low coverage (2x2) overlayer has been observed. The symmetry of the unit cell in this layer suggests that the CO is adsorbed in the 3-fold hollow sites. There were also two higher coverage surface structures with ({radical}7x{radical}7) unit cells. One of these is composed of trimers of CO and has three CO molecules in each unit cell. The other structure has an additional CO molecule, making a total of four. This extra CO sits on a top site.
Date: August 1, 1999
Creator: Cernota, Paul D.
Partner: UNT Libraries Government Documents Department

Baseline milestone HWVP-87-V110202F: Preliminary evaluation of noble metal behavior in the Hanford waste vitrification plant reference glass HW-39

Description: The precipitation and aggregation of ruthenium (Ru), rhodium (RLh) and palladium (Pd) in the Hanford Waste Vitrification Plant (HWVP) low chromium reference glass HLW-39 were investigated to determine if there is a potential for formation of a noble metal sludge in the HWVP ceramic melter. Significant noble metal accumulations on the floor of the melter will result in the electrical shorting of the electrodes and premature failure of the melter. The purpose of this study was to obtain preliminary information on the characteristics of noble metals in a simulated HWVP glass. Following a preliminary literature view to obtain information concerning the noble metals behavior, a number of variability studies were initiated. The effects of glass redox conditions, melt temperature, melting time and noble metal concentration on the phase characteristics of these noble metals were examined.
Date: March 1, 1996
Creator: Geldart, R.W.; Bates, S.O. & Jette, S.J.
Partner: UNT Libraries Government Documents Department