17,011 research outputs found
The coordination chemistry of saturated molecules
Our understanding of bonding in transition metal complexes, as well as our ability to use that understanding in the synthesis and application of new species, has evolved over the last 100 years; and in some sense this special feature on the coordination chemistry of saturated molecules may be considered to represent its culmination. The nature of complexes between transition metal ions and neutral molecules such as ammonia was first correctly described by Werner around the beginning of the 20th century. Interpretations in terms of electronic bonding theories followed soon after. The key feature, of course, is the availability of a low-energy filled "lone pair" orbital available for donation to a vacant orbital on the electron-accepting metal ion
A MULTIATTRIBUTE UTILITY ANALYSIS OF TECHNOLOGICAL CHOICE IN THE CALIFORNIA WILD RICE INDUSTRY
Technological choice and competitive strategy issues are reviewed and then a framework for choosing between two competing technologies is proposed.The two competing technologies differ in their ability to store and process wild rice over a marketing year. The traditional technologies requires almost immediate processing of the harvested wild rice while the experimental technology allows harvested wild rice to be stored and processed over the course of the marketing year. Technological choice is explored using multiattribute utility analysis and two economic evaluations. The economic evaluations are payback period analysis and internal rate of return analysis given uncertain demand conditions. The experimental technology is shown to be the dominant technological choice under both multiattribute utility analysis and the economic analyses.Research and Development/Tech Change/Emerging Technologies,
Electrophilic Aromatic Nitrosation. Isolation and X-ray Crystallography of the Metastable NO\u3csup\u3e+\u3c/sup\u3e Complex With Nitrosoarene
Isolation of the unstable 1â¶1 complex of 4-nitrosoanisole with NO+PF6â allows its precise X-ray structural characterization. The charge-transfer crystal is formed via strong NâŻN coordination [the distance of 1.938(5) Ă
corresponding to a Ï-bond order of â0.2] in the mean plane of the planar 4-nitrosoanisole donor. Thorough analysis of its molecular geometry in terms of valence resonance and MO schemes reveals a strong charge polarization with a local negative charge localized on the nitroso group and a local positive charge distributed over the adjacent p-methoxybenzyl moiety. Such a charge distribution accommodates the well-known passivation of nitrosoarenes to multiple nitrosation and explains the ease of demethylation of the complex. Comparison of a variety of nitroso- and nitroarene structures has shown that the nitrosoarene experiences a much stronger quinoidal distortion of the aromatic ring as compared with the latter. This indicates a stronger electron-withdrawing effect of the nitroso group relative to that of the nitro group. The weakened aromatic resonance in the nitrosoarenes could be responsible for the observed slower rate and the measurable isotope effect in electrophilic nitrosation as opposed to nitration
Intra- and Intermolecular CâH Activation by Bis(phenolate)pyridineiridium(III) Complexes
A bis(phenolate)pyridine pincer ligand (henceforth abbreviated as ONO) has been employed to support a variety of iridium complexes in oxidation states I, III, and IV. Complexes (ONO)IrL_2Me (L = PPh_3, PEt_3) react with I_2 to cleave the IrâC bond and liberate MeI, apparently via a mechanism beginning with electron transfer to generate an intermediate Ir(IV) complex, which can be isolated and characterized for the case L = PEt_3. The PPh_3 complex is transformed in benzene at 65 °C to the corresponding phenyl complex, with loss of methane, and subsequently to a species resulting from metalation of a PPh_3 ligand. Labeling and kinetics studies indicate that PPh_3 is the initial site of CâH activation, even though the first observed product is that resulting from intermolecular benzene activation. CâH activation of acetonitrile has also been observed
Activation of a CâH Bond in Indene by [(COD)Rh(ÎŒ_2-OH)]_2
The air- and water-tolerant hydroxy-bridged rhodium dimer [(COD)Rh(ÎŒ_2-OH)]_2 cleanly activates the aliphatic CâH bond in indene to generate [(COD)Rh(η^3-indenyl)]. The mechanism involves direct coordination of indene to the dimer followed by rate-determining CâH bond cleavage, in contrast to the previously reported analogous reactions of [(diimine)M(ÎŒ_2-OH)]_2^(2+) (M = Pd, Pt), for which the dimer must be cleaved before rate-determining displacement of solvent by indene. Another difference is observed in the reactions with indene in the presence of acid: the Rh system generates a stable η^6-indene 18-electron cation, [(COD)Rh(η^6-indene)]+, that is not available for Pd and Pt, which instead form the η^3-indenyl CâH activation products. The crystal structure of [(COD)Rh(η^6-indene)] is reported
An Analysis of Sportsman Activity Data Collection Methods for North Dakota
Resource /Energy Economics and Policy,
Beyond rules: The next generation of expert systems
The PARAGON Representation, Management, and Manipulation system is introduced. The concepts of knowledge representation, knowledge management, and knowledge manipulation are combined in a comprehensive system for solving real world problems requiring high levels of expertise in a real time environment. In most applications the complexity of the problem and the representation used to describe the domain knowledge tend to obscure the information from which solutions are derived. This inhibits the acquisition of domain knowledge verification/validation, places severe constraints on the ability to extend and maintain a knowledge base while making generic problem solving strategies difficult to develop. A unique hybrid system was developed to overcome these traditional limitations
A Versatile Ligand Platform that Supports Lewis Acid Promoted Migratory Insertion
A helping hand: Incorporation of Groupâ
2 Lewis acids into a macrocycle appended to a phosphine ligand attached to a rhenium carbonyl complex promotes otherwise unfavorable transformations of coordinated CO (see scheme; M=Ca, Sr). These Lewis acids form relatively weak M-O bonds, thereby enabling release of organic products from the metal center
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