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PubMed2006

New ruthenium nitrosyl complexes with tris(1-pyrazolyl)methane (tpm) and 2,2'-bipyridine (bpy) coligands. Structure, spectroscopy, and electrophilic and nucleophilic reactivities of bound nitrosyl.

The new compound [Ru(bpy)(tpm)NO](ClO4)3 [tpm = tris(1-pyrazolyl)methane; bpy = 2,2'-bipyridine] has been prepared in a stepwise procedure that involves the conversion of [Ru(bpy)(tpm)Cl]+ into the aqua and nitro intermediates, followed by acidification. The diamagnetic complex crystallizes to exhibit distorted octahedral geometry around the metal, with the Ru-N(O) bond length 1.774(12) A and the RuNO angle 179.1(12) degrees , typical for a {RuNO}6 description. The [Ru(bpy)(tpm)NO]3+ ion (I) has been characterized by 1H NMR and IR spectroscopies (nu(NO) = 1959 cm(-1)) and through density functional theory calculations. Intense electronic transitions in the 300-350-nm region are assigned through time-dependent (TD)DFT as intraligand pi --> pi for bpy and tpm. The dpi --> pi(bpy) metal-to-ligand charge-transfer transitions appear at higher energies. Aqueous cyclic voltammetric studies show a reversible wave at 0.31 V (vs Ag/AgCl, 3 M Cl-), which shifts to 0.60 V in MeCN, along with the onset of a wave of an irreversible process at -0.2 V. The waves are assigned to the one- and two-electron reductions centered at the NO ligand, leading to species with {RuNO}(7) and {RuNO}(8) configurations, respectively. Controlled potential reduction of I in MeCN led to the [Ru(bpy)(tpm)NO]2+ ion (II), revealing a significant downward shift of nu(NO) to 1660 cm(-1) as well as changes in the electronic absorption bands. II was also characterized by electron paramagnetic resonance, showing an anisotropic signal at 110 K that arises from an S = 1/2 electronic ground state; the g-matrix components and hyperfine coupling tensor resemble the behavior of related {RuNO}7 complexes. Both I and II were characterized through their main reactivity modes, electrophilic and nucleophilic, respectively. The addition of OH- into I generated the nitro complex, with k(OH) = 3.05 x 10(6) M(-1) s(-1) (25 degrees C). This value is among the highest obtained for related nitrosyl complexes and correlates with ENO+/NO, the one-electron redox potential. Complex II is a robust species toward NO release, although a conversion to I was observed in the presence of O2. This reaction afforded a second-order rate law with k = 3.5 M(-1) s(-1) (25 degrees C). The stabilization of the NO radical complex is attributed to the high positive charge of the precursor and to the geometrical and electronic structure as determined by the neutral tpm ligand.

2,2'-Dipyridyl↗
PubMed2007

Syntheses, structures, spectroscopy, and chromotropism of new complexes arising from the reaction of nickel(II) nitrate with diphenyl(dipyrazolyl)methane.

The complexes [(dpdpm)Ni(2-NO3)2] (1), [(dpdpm)Ni(2-NO3)(1-NO3)(CH3CN)] (2), [(dpdpm)2Ni(1-NO3)(H2O)]NO3 (3), and [(dpdpm)2Ni(H2O)2][NO3]2 (4) (dpdpm = diphenyl(dipyrazolyl)methane, Ph2C(C3N2H3)2), have been prepared and characterized by IR and UV-vis-NIR spectroscopy and X-ray diffraction studies. X-ray studies have confirmed that complexes 1-4 all adopt variously distorted octahedral structures in the solid state, the largest distortions arising from the small bite-angle of the bidentate nitrate ligand in 1 and 2. Magnetic moment measurements indicate that these solids are paramagnetic with two unpaired electrons. The solution 1H NMR data show that the paramagnetism is maintained in solution. Absorption spectra of 1-4 show three main bands in the region of 350-1000 nm representing spin allowed (d-d) transitions from the ground state 3A2g to the excited states 3T2g, 3T1g(3F), and 3T1g(3P). A weak shoulder was also detected at about 700-800 nm in most spectra, representing spin-forbidden transitions 3A2g 1Eg. A comparison of the crystal field parameters 10Dq and B for 1-4 to the corresponding values for related complexes indicated that these parameters are fairly insensitive to structural variations within this family of complexes. The 10Dq/B ratios show greater variations, but no clear correlations are apparent between 10Dq/B and such structural features as the nature of ligator atoms (N:O ratio), the bonding mode of the nitrate ligand, or the overall charge. Complexes 1 (green) and 2 (blue) interconvert as a function of temperature (solutions and solid samples), concentration of CH3CN (solutions), or CH3CN vapor pressure (solid samples).

Acetonitriles↗
PubMed2003

Is the ruthenium analogue of compound I of cytochrome p450 an efficient oxidant? A theoretical investigation of the methane hydroxylation reaction.

High-valent metal-oxo complexes catalyze C-H bond activation by oxygen insertion, with an efficiency that depends on the identity of the transition metal and its oxidation state. Our study uses density functional calculations and theoretical analysis to derive fundamental factors of catalytic activity, by comparison of a ruthenium-oxo catalyst with its iron-oxo analogue toward methane hydroxylation. The study focuses on the ruthenium analogue of the active species of the enzyme cytochrome P450, which is known to be among the most potent catalysts for C-H activation. The computed reaction pathways reveal one high-spin (HS) and two low-spin (LS) mechanisms, all nascent from the low-lying states of the ruthenium-oxo catalyst (Ogliaro, F.; de Visser, S. P.; Groves, J. T.; Shaik, S. Angew. Chem. Int. Ed. 2001, 40, 2874-2878). These mechanisms involve a bond activation phase, in which the transition states (TS's) appear as hydrogen abstraction species, followed by a C-O bond making phase, through a rebound of the methyl radical on the metal-hydroxo complex. However, while the HS mechanism has a significant rebound barrier, and hence a long lifetime of the radical intermediate, by contrast, the LS ones are effectively concerted with small barriers to rebound, if at all. Unlike the iron catalyst, the hydroxylation reaction for the ruthenium analogue is expected to follow largely a single-state reactivity on the LS surface, due to a very large rebound barrier of the HS process and to the more efficient spin crossover expected for ruthenium. As such, ruthenium-oxo catalysts (Groves, J. T.; Shalyaev, K.; Lee, J. In The Porphyrin Handbook; Biochemistry and Binding: Activation of Small Molecules, Vol. 4; Kadish, K. M., Smith, K. M., Guilard, R., Eds.; Academic Press: New York, 2000; pp 17-40) are expected to lead to more stereoselective hydroxylations compared with the corresponding iron-oxo reactions. It is reasoned that the ruthenium-oxo catalyst should have larger turnover numbers compared with the iron-oxo analogue, due to lesser production of suicidal side products that destroy the catalyst (Ortiz de Montellano, P. R.; Beilan, H. S.; Kunze, K. L.; Mico, B. A. J. Biol. Chem. 1981, 256, 4395-4399). The computations reveal also that the ruthenium complex is more electrophilic than its iron analogue, having lower hydrogen abstraction barriers. These reactivity features of the ruthenium-oxo system are analyzed and shown to originate from a key fundamental factor, namely, the strong 4d(Ru)-2p(O,N) overlaps, which produce high-lying pi(Ru-O), sigma(Ru-O), and sigma(Ru-N) orbitals and thereby to lead to a preference of ruthenium for higher-valent oxidation states with higher electrophilicity, for the effectively concerted LS hydroxylation mechanism, and for less suicidal complexes. As such, the ruthenium-oxo species is predicted to be a more robust catalyst than its iron-oxo analogue.

Biomimetic Materials↗
PubMed2005

Design of a chiral mesoporous silica and its application as a host for stereoselective di-pi-methane rearrangements.

[reaction: see text] A chiral periodic mesoporous organosilica (ChiMO) was prepared, in which a 1,2-bis-(ureido)cyclohexyl linker (38 wt %) is introduced into the walls of the hybrid organic-inorganic material. This silica was used as a host for 11-formyl-12-methyldibenzobarrelene (2), and the stereoselectivity of the di-pi-methane rearrangement of 2 within this host-guest complex was studied. At low conversions, the only product was the corresponding dibenzosemibullvalene. An enantiomeric excess of 24% at 11% conversion was obtained using the ChiMO as host. These values compare well with those achieved using a system based on conventional faujasites (LiY and NaY) as hosts incorporating a chiral auxiliary. We tested S-phenylglycine, S-proline, S-camphanic acid, and S-mandelic acid as chiral auxiliaries. In contrast to the behavior of the ChiMO material, adsorption of dibenzobarrelene in purely siliceous mesoporous MCM-41 silica (3.2 nm pore size) containing ephedrine failed, a failure that can be explained as arising from the large internal silanol population and high hydrophilicity of the siliceous MCM-41 sample.

Methane↗
PubMed2006

Methane activation by laser-ablated V, Nb, and Ta atoms: Formation of CH3-MH, CH2=MH2, CHMH3-, and (CH3)2MH2.

Methane activation by group 5 transition-metal atoms in excess argon and the matrix infrared spectra of reaction products have been investigated. Vanadium forms only the monohydrido methyl complex (CH3-VH) in reaction with CH4 and upon irradiation. On the other hand, the heavier metals form methyl hydride and methylidene dihydride complexes (CH3-MH and CH2=MH2) along with the methylidyne trihydride anion complexes (CHMH3-). The neutral products, particularly the methylidene complex, increase markedly on irradiation whereas the anionic product depletes upon UV irradiation or addition of a trace of CCl4 or CBr4 to trap electrons. Other absorptions that emerge on irradiation and annealing increase markedly at higher precursor concentration and are attributed to a higher-order product ((CH3)2MH2)). Spectroscopic evidence suggests that the agostic Nb and Ta methylidene dihydride complexes have two identical metal-hydrogen bonds.

Argon↗
PubMed2006

Effects of confinement on the adsorption behavior of methane in high-silica zeolites.

Adsorption isotherms of methane on high-silica zeolites at ambient temperature and up to high pressure were experimentally measured. The isotherms were analyzed on the basis of thermodynamics and statistical mechanics, and the relationship between microscopic properties and the macroscopic adsorption behavior was investigated. A comparison between the confined and unconfined phases revealed that molecular motion is restricted in the pores. As a result, the adsorbed phase is entropically destabilized, which cannot be neglected in comparison with the energetical stabilization that occurs as a result of the solid-molecule interaction. Our findings also indicate that the smaller slope (drho/d ln p) of the adsorption isotherms compared to that of the isotherm of the bulk at the same density is due to the smaller intermolecular interaction in the pores. The pore-size dependence is indicated not only in solid-molecule interactions but also in intermolecular interactions and molecular motion. Of these, the solid-molecule interactions strongly influence the adsorption behaviors in pores of different sizes. The origin of the restriction of molecular motion in the pores is well-explained by the one-dimensional transition and two-dimensional vibration (1D-trans, 2D-vib) model.

Adsorption↗
PubMed2006

The reactivity of all-metal aromatic complexes: a theoretical investigation on the methane activation reaction.

The recent finding of all-metal aromaticity enlightens us to explore the reactivity of all-metal aromatic complexes. The methane activation reaction was chosen for this purpose. The whole catalysis process of all-metal aromatics was investigated by theoretical calculation. The results reveal that the reaction barriers with all-metal aromatic complexes are far lower than that without any catalysts. All-metal aromatic complexes are predicted to have potential to be used as catalysts for the first time.

Aluminum↗
PubMed2004

Design of new materials for methane storage.

One of the strategic goals of the modern automobile manufacturing industry is to replace gasoline and diesel with alternative fuels such as natural gas. In this report, we elucidate the desired characteristics of an optimal adsorbent for gas storage. The U.S. Department of Energy has outlined several requirements that adsorbents must fulfill for natural gas to become economically viable, with a key criterion being the amount adsorbed at 35 bar. We explore the adsorption characteristics of novel metal-organic materials (IRMOFs and molecular squares) and contrast them with the characteristics of two zeolites, MCM-41, and different carbon nanotubes. Using molecular simulations, we uncover the complex interplay of the factors influencing methane adsorption, especially the surface area, the capacity or free volume, the strength of the energetic interaction, and the pore size distribution. We also explain the extraordinary adsorption properties of IRMOF materials and propose new, not yet synthesized IRMOF structures with adsorption characteristics that are predicted to exceed the best experimental results to date by up to 36%.

Adsorption↗
PubMed2004

Ultrasound-assisted polyol method for the preparation of SBA-15-supported ruthenium nanoparticles and the study of their catalytic activity on the partial oxidation of methane.

Metallic Ru nanoparticles have been successfully produced and incorporated into the pores of SBA-15 in situ employing a simple ultrasound-assisted polyol method. The product has been confirmed by X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy, where ultrasound provides both the energy for the reduction of the Ru(III) ion and the driving force for the loading of the Ru(0) nanoparticles into the SBA-15 pores. An ultrasound-assisted insertion mechanism has been proposed based on the microjets and shake-wave effect of the collapsed bubbles. The catalytic properties of the SBA-15-supported Ru nanoparticles have been tested by the partial oxidization of methane and show very high activity and high CO selectivity.

Catalysis↗
PubMed2000

Adaptation of methane formation and enzyme contents during growth of Methanobacterium thermoautotrophicum (strain deltaH) in a fed-batch fermentor.

During growth of Methanobacterium thermoautotrophicum in a fed-batch fermentor, the cells are confronted with a steady decrease in the concentration of the hydrogen energy supply. In order to investigate how the organism responds to these changes, cells collected during different growth phases were examined for their methanogenic properties. Cellular levels of the various methanogenic isoenzymes and functionally equivalent enzymes were also determined. Cells were found to maintain the rates of methanogenesis by lowering their affinity for hydrogen: the apparent Km(H2) decreased in going from the exponential to the stationary phase. Simultaneously, the maximal specific methane production rate changed. Levels of H2-dependent methenyl-tetrahydromethanopterin dehydrogenase (H2-MDH) and methyl coenzyme M reductase isoenzyme II (MCR II) decreased upon entry of the stationary phase. Cells grown under conditions that favored MCR II expression had higher levels of MCR II and H2-MDH, whereas in cells grown under conditions favoring MCR I, levels of MCR II were much lower and the cells had an increased affinity for hydrogen throughout the growth cycle. The use of thiosulfate as a medium reductant was found to have a negative effect on levels of MCR II and H2-MDH. From these results it was concluded that M. thermoautotrophicum responds to variations in hydrogen availability and other environmental conditions (pH, growth temperature, medium reductant) by altering its physiology. The adaptation includes, among others, the differential expression of the MDH and MCR isoenzymes.

Adaptation, Physiological↗
PubMed2003

Biotic landfill cover treatments for mitigating methane emissions.

Landfill methane (CH4) emissions have been cited as one of the anthropogenic gas releases that can and should be controlled to reduce global climate change. This article reviews recent research that identifies ways to enhance microbial consumption of the gas in the aerobic portion of a landfill cover. Use of these methods can augment CH4 emission reductions achieved by gas collection or provide a sole means to consume CH4 at small landfills that do not have active gas collection systems. Field studies indicate that high levels of CH4 removal can be achieved by optimizing natural soil microbial processes. Further, during biotic conversion, not all of the CH4 carbon is converted to carbon dioxide (CO2) gas and released to the atmosphere; some of it will be sequestered in microbial biomass. Because biotic covers can employ residuals from other municipal processes, financial benefits can also accrue from avoided costs for residuals disposal.

Air Pollution↗
PubMed2004

Optimization of methanol biosynthesis from methane using Methylosinus trichosporium OB3b.

Methylosinus trichosporium OB3b oxidized methane to methanol in the presence of a high concentration of Cu2+. Further oxidation of methanol to formaldehyde was prevented by adding 200 mM NaCl which acted as a methanol dehydrogenase H inhibitor. The bacterium, 0.6 mg dry cell ml(-1), in methane/air (1:4, v/v) at 25 degrees C in 12.9 mM phosphate buffer (pH 7) containing 20 mM sodium formate and 200 mM NaCl accumulated 7.7 mM methanol over 36 h.

Cell Culture Techniques↗
PubMed1987

Coloration and darkening of methane clathrate and other ices by charged particle irradiation: applications to the outer solar system.

Methane clathrate is expected to be an important carbon-containing ice in the outer solar system. We investigate the effect of electron irradiation by coronal discharge on several simple hydrocarbons enclathrated in or mixed with H2O or H2O+NH3 in simulation of the effects of the solar wind, planetary magnetospheric particles, and cosmic rays on surfaces containing these ices in the outer solar system and interstellar space. H2O+CH4 clathrate, H2O+C2H6, H2O+CH4+NH3, H2O+C2H6+NH3, and H2O+C2H2 are all initially white ices, and all produce yellowish to brownish organic products upon charged particles irradiation. Significant coloration occurs with doses of 10(9) erg cm-2, corresponding to short interplanetary irradiation times. Uranian magnetospheric electrons penetrate to approximately 1 mm depth and deposit this dose in 8, 30, 65, 200, and 500 years into the surfaces of Miranda, Ariel, Umbriel, Titania, and Oberon, respectively. Further irradiation of the laboratory ice surface results in a progressive darkening and a more subdued color. For a conversion efficiency to solids G approximately equal to 1 molecule keV-1, the upper limit for the time for total destruction of CH4 and other simple hydrocarbons in the upper 1 mm is 5 x 10(4) years (Miranda) to 3 x 10(6) years (Oberon). Remote detection of CH4 is possible only when its replenishment rate exceeds the destruction rate at the depth probed by spectroscopy. Reflection spectroscopy or irradiated H2O+CH4 frost is compared with the spectra of several outer solar system objects and to other relevant organic and inorganic materials. Ultraviolet-visible and infrared transmission spectroscopy of the postirradiation residues is presented. Persistence of color and of CH4 ice bands on Triton and Pluto suggests ongoing surface activity and/or atmospheric haze. Over 4 x 10(9) year time scales, > or = 10 m of satellite and cometary surface material is processed by cosmic rays to a radiation-hardened ice-tholin mixture devoid of CH4. Preaccretional chemistry, exogenous materials, and endogenous organic chemistry all contribute to the spectral properties of icy satellites which accreted simple CH(O) molecules. Radiation darkening traces the deposition of mobilized or impact-exposed carbon-bearing volatiles on these satellites. More exhaustive experiments are necessary to work out the detailed relationships between initial composition, exposure age, and color/albedo.

Ammonia↗
PubMed1980

New findings in methane-utilizing bacteria highlight their importance in the biosphere and their commercial potential.

Recent results, showing that the ubiquitous methane-utilizing bacteria (methanotrophs) can partially oxidize and, in some cases, extensively metabolize complex organic compounds, call for a reappraisal of their role in the cycling of elements in the biosphere. Possible environmental implications and opportunities for industrial exploitation are discussed.

Biological Evolution↗
PubMed2004

Release of methane from a volcanic basin as a mechanism for initial Eocene global warming.

A 200,000-yr interval of extreme global warming marked the start of the Eocene epoch about 55 million years ago. Negative carbon- and oxygen-isotope excursions in marine and terrestrial sediments show that this event was linked to a massive and rapid (approximately 10,000 yr) input of isotopically depleted carbon. It has been suggested previously that extensive melting of gas hydrates buried in marine sediments may represent the carbon source and has caused the global climate change. Large-scale hydrate melting, however, requires a hitherto unknown triggering mechanism. Here we present evidence for the presence of thousands of hydrothermal vent complexes identified on seismic reflection profiles from the Vøring and Møre basins in the Norwegian Sea. We propose that intrusion of voluminous mantle-derived melts in carbon-rich sedimentary strata in the northeast Atlantic may have caused an explosive release of methane--transported to the ocean or atmosphere through the vent complexes--close to the Palaeocene/Eocene boundary. Similar volcanic and metamorphic processes may explain climate events associated with other large igneous provinces such as the Siberian Traps (approximately 250 million years ago) and the Karoo Igneous Province (approximately 183 million years ago).

Animals↗
PubMed2005

Atmospheric methane at Zeppelin Station in Ny-Alesund: presentation and analysis of in situ measurements.

In situ methane (CH(4)) measurement techniques and data from the Zeppelin Station in Ny-Alesund on Svalbard (N 78 degrees 54' E 11 degrees 53') on Mt. Zeppelin (475 m.a.s.l) are presented. The data span the time period from October 1998 to December 2003, though not continuously. The daily mean was calculated from 96 samples per day which are analysed by gas chromatography with flame ionisation detection. Details of the experimental methods and procedures are given. A harmonic function is fitted to the data with a constant trend and seasonal amplitude. The data are also presented in a regression plot showing the difference between the in situ measurements and flask measurements from the National Oceanic and Atmospheric Administration of the Climate Monitoring and Diagnostics Laboratory (NOAA/CMDL) in Boulder, Colorado (http://www.cmdl.noaa.gov/). The Zeppelin data show typical Arctic air characteristics with wintertime pollution episodes from Europe and Russia and a relatively calm summer state.

Air Movements↗