Preparation, Structure, and Reactivity of Nonstabilized Organoiron Compounds. Implications for Iron-Catalyzed Cross Coupling Reactions

A series of unprecedented organoiron complexes of the formal oxidation states −2, 0, +1, +2, and +3 is presented, which are largely devoid of stabilizing ligands and, in part, also electronically unsaturated (14-, 16-, 17- and 18-electron counts). Specifically, it is shown that nucleophiles unable to undergo β-hydride elimination, such as MeLi, PhLi, or PhMgBr, rapidly reduce Fe(3+) to Fe(2+) and then exhaustively alkylate the metal center. The resulting homoleptic organoferrate complexes [(Me4Fe)(MeLi)][Li(OEt2)]2 (3) and [Ph4Fe][Li(Et2O)2][Li(1,4-dioxane)] (5) could be characterized by X-ray crystal structure analysis. However, these exceptionally sensitive compounds turned out to be only moderately nucleophilic, transferring their organic ligands to activated electrophiles only, while being unable to alkylate (hetero)aryl halides unless they are very electron deficient. In striking contrast, Grignard reagents bearing alkyl residues amenable to β-hydride elimination reduce FeXn (n = 2, 3) to clusters of the formal composition [Fe(MgX)2]n. The behavior of these intermetallic species can be emulated by structurally well-defined lithium ferrate complexes of the type [Fe(C2H4)4][Li(tmeda)]2 (8), [Fe(cod)2][Li(dme)]2 (9), [CpFe(C2H4)2][Li(tmeda)] (7), [CpFe(cod)][Li(dme)] (11), or [Cp*Fe(C2H4)2][Li(tmeda)] (14). Such electron-rich complexes, which are distinguished by short intermetallic Fe−Li bonds, were shown to react with aryl chlorides and allyl halides; the structures and reactivity patterns of the resulting organoiron compounds provide first insights into the elementary steps of low valent iron-catalyzed cross coupling reactions of aryl, alkyl, allyl, benzyl, and propargyl halides with organomagnesium reagents. However, the acquired data suggest that such C−C bond formations can occur, a priori, along different catalytic cycles shuttling between metal centers of the formal oxidation states Fe(+1)/Fe(+3), Fe(0)/Fe(+2), and Fe(−2)/Fe(0). Since these different manifolds are likely interconnected, an unambiguous decision as to which redox cycle dominates in solution remains difficult, even though iron complexes of the lowest accessible formal oxidation states promote the reactions most effectively

The electronic structure of pyrazine. Configuration interaction calculations using an extended basis

Extensive ab initio double zeta basis set configuration interaction calculations have been carried out on the nπ^∗ and ππ^∗ states of pyrazine as well as on the low‐lying n and π cations. The calculations corroborate the validity of the valence bond (VB) model for the interaction of lone pair excitations proposed earlier by Wadt and Goddard. Good agreement (errors of ∼0.2 eV) with experiment is obtained (except for the higher‐lying 1ππ∗ states that possess significant ionic character). The calculations indicate that the order of increasing ionization potentials is ^2A_g(n), 2B_(1g)(π), 2B_(1u)(n), and ^2B_(2g)(π). The forbidden 1 ^1B_(2g)(nπ^∗) state is predicted to be 1.30 eV above the allowed 1^ 1B_(3u)(nπ^∗) state. Finally, the calculations indicate that the adiabatic excitation energies to the 1^ 3B_1(nπ^∗) and 1^ 3A_1(ππ^∗) states in pyridine should be nearly degenerate at ∼3.6 eV

Prediction of the Size Distributions of Methanol-Ethanol Clusters Detected in VUV Laser/Time-of-flight Mass Spectrometry

The size distributions and geometries of vapor clusters equilibrated with methanol−ethanol (Me−Et) liquid mixtures were recently studied by vacuum ultraviolet (VUV) laser time-of-flight (TOF) mass spectrometry and density functional theory (DFT) calculations (Liu, Y.; Consta, S.; Ogeer, F.; Shi, Y. J.; Lipson, R. H. Can. J. Chem. 2007, 85, 843−852). On the basis of the mass spectra recorded, it was concluded that the formation of neutral tetramers is particularly prominent. Here we develop grand canonical Monte Carlo (GCMC) and molecular dynamics (MD) frameworks to compute cluster size distributions in vapor mixtures that allow a direct comparison with experimental mass spectra. Using the all-atom optimized potential for liquid simulations (OPLS-AA) force field, we systematically examined the neutral cluster size distributions as functions of pressure and temperature. These neutral cluster distributions were then used to derive ionized cluster distributions to compare directly with the experiments. The simulations suggest that supersaturation at 12 to 16 times the equilibrium vapor pressure at 298 K or supercooling at temperature 240 to 260 K at the equilibrium vapor pressure can lead to the relatively abundant tetramer population observed in the experiments. Our simulations capture the most distinct features observed in the experimental TOF mass spectra: Et3H+ at m/z = 139 in the vapor corresponding to 10:90% Me−Et liquid mixture and Me3H+ at m/z = 97 in the vapors corresponding to 50:50% and 90:10% Me−Et liquid mixtures. The hybrid GCMC scheme developed in this work extends the capability of studying the size distributions of neat clusters to mixed species and provides a useful tool for studying environmentally important systems such as atmospheric aerosols

Developmental Mode in Opisthobranch Molluscs from the Northeast Pacific Ocean: Additional Species from Southern California and Supplemental Data

We document development type for 33 species of benthic opisthobranch gastropods – 15 for the first time – collected mainly from the Southern California Bight. Fourteen of the newly examined species had planktotrophic development, while the dorid nudibranch Atagema alba had capsular metamorphic development, the first example of direct development in a non-dendrodoridid nudibranch known from the northeast Pacific Ocean. For the remaining 18 species our new data are either consistent with earlier determinations of development type, or confirm previous inferences. The new data also broaden geographic coverage for some species, and for the sacoglossan Stiliger fuscovittatus and the nudibranch Melibe leonina, suggest that egg size is inversely related to temperature. We correct the previous erroneous identification of nephrocysts as eyespots in the hatching planktotrophic larvae of the nudibranchs Tritonia festiva and Janolus fuscus. These results further highlight the predominance of planktotrophic development in benthic opisthobranchs from the northeast Pacific Ocean

Recent Legal Literature

Beale: The Law of Innkeepers and Hotels, including other Public Houses, Theatres, Sleeping Cars; Beale: The Law of Railroad Rate Regulation, with special reference to American Legislation; Moore: A Treatise on the Law of Carriers; Bernard: The First Year of Roman Law; Holland: The Elements of Jurisprudence; Wilcox: Foibles of the Bench; Wigmore (ed.): A Selection of Cases on Evidence for the Use of Students of Law; Fairlie: Local Government in Counties, Towns and Villages; Hirschl: Trial Tactics. A Treatment of the Methods of Conducting Litigatio

Ligand Lone-Pair Influence on Hydrocarbon C-H Activation: A Computational Perspective

Mid to late transition metal complexes that break hydrocarbon C-H bonds by transferring the hydrogen to a heteroatom ligand while forming a metal-alkyl bond offer a promising strategy for C-H activation. Here we report a density functional (B3LYP, M06, and X3LYP) analysis of cis-(acac)_2MX and TpM(L)X (M=Ir, Ru, Os, and Rh; acac=acetylacetonate, Tp=tris(pyrazolyl)-borate; X=CH_3, OH, OMe, NH_2, and NMe_2) systems for methane C-H bond activation reaction kinetics and thermodynamics.We address the importance of whether a ligand lone pair provides an intrinsic kinetic advantage through possible electronic d_π-p_π repulsions for M-OR and M-NR_2 systems versus M-CH_3 systems. This involves understanding the energetic impact of the X ligand group on ligand loss, C-H bond coordination, and C-H bond cleavage steps as well as understanding how the nucleophilicity of the ligand X group, the electrophilicity of the transition metal center, and cis-ligand stabilization effect influence each of these steps.We also explore how spectator ligands and second- versus third-row transition metal centers impact the energetics of each of these C-H activation steps

Urban socioeconomic inequality and biodiversity often converge, but not always: A global meta-analysis

It is through urban biodiversity that the majority of humans experience nature on a daily basis. As cities expand globally, it is increasingly important to understand how biodiversity is shaped by human decisions, institutions, and environments. In some cities, research has documented convergence between high socioeconomic status (SES) and high species diversity. Yet, other studies show that residents with low SES live amid high biodiversity or that SES and biodiversity appear unrelated. This study examines the conditions linked to varying types of relationships between SES and biodiversity. We identified and coded 84 case studies from 34 cities in which researchers assessed SES-biodiversity relationships. We used fuzzy-set Qualitative Comparative Analysis (fsQCA) to evaluate combinations of study design and city-level conditions that explain why SES-biodiversity relationships vary city to city and between plants and animals. While the majority of cases demonstrated increased biodiversity in higher SES neighborhoods, we identified circumstances in which inequality in biodiversity distribution was ameliorated or negated by disturbance, urban form, social policy, or collective human preference. Overall, our meta-analysis highlights the contributions of residential and municipal decisions in differentially promoting biodiversity along socioeconomic lines, situated within each city’s environmental and political context. Through identifying conditions under which access to biodiversity is more or less unequal, we call attention to outstanding research questions and raise prospects for better promoting equitable access to biodiversity

No-till can reduce the risk of heat stress in wheat

Non-Peer ReviewedNo-till farming (NT) is increasing in the Canadian Prairies in recent years because of the economic and environment benefits and its potential to sequester atmospheric carbon into the soil. Because surface residue and stubble act as insulation and impedes the exchange rate of thermal energy between the soil and the atmosphere, lower root-zone temperatures in the NT fields compared with that in the conventionally tilled (CT) fields were widely observed in the spring. Some studies found that low temperatures under NT persisted to the mid-season or throughout the whole growing season. Little attention, however, has been paid to the impact of the cooling effect of NT on the grain yield of wheat. The objective of this study was to investigate if NT could alleviate heat stress and benefit yield

Comparison of the Fermi-surface topologies of kappa-(BEDT-TTF)_2 Cu(NCS)_2 and its deuterated analogue

We have measured details of the quasi one-dimensional Fermi-surface sections in the organic superconductor kappa-(BEDT-TTF)_2 Cu(NCS)_2 and its deuterated analogue using angle-dependent millimetre-wave techniques. There are significant differences in the corrugations of the Fermi surfaces in the deuterated and undeuterated salts. We suggest that this is important in understanding the inverse isotope effect, where the superconducting transition temperature rises on deuteration. The data support models for superconductivity which invoke electron-electron interactions depending on the topological properties of the Fermi surface

Strongly correlated wave functions for artificial atoms and molecules

A method for constructing semianalytical strongly correlated wave functions for single and molecular quantum dots is presented. It employs a two-step approach of symmetry breaking at the Hartree-Fock level and of subsequent restoration of total spin and angular momentum symmetries via Projection Techniques. Illustrative applications are presented for the case of a two-electron helium-like single quantum dot and a hydrogen-like quantum dot molecule.Comment: 9 pages. Revtex with 2 GIF and 1 EPS figures. Published version with extensive clarifications. A version of the manuscript with high quality figures incorporated in the text is available at http://calcite.physics.gatech.edu/~costas/qdhelproj.html For related papers, see http://www.prism.gatech.edu/~ph274c