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

In situ mineralogical-chemical analysis of Martian materials at landing/roving sites by active and passive remote sensing methods

Remote sensing of the Martian surface from the ground and from orbiting spacecraft has provided some first-order insight into the mineralogical-chemical composition and the weathering state of Martian surface materials. Much more detailed information can be gathered from performing such measurements in situ at the landing sites or from a rover in combination with analogous measurements from orbit. Measurements in the wavelength range of approximately 0.3 to 12.0 micrometers appear to be suitable to characterize much of the physical, mineralogical, petrological, and chemical properties of Martian surface materials and the weathering and other alteration processes that have acted on them. It is of particular importance to carry out measurements at the same time over a broad wavelength range since the reflectance signatures are caused by different effects and hence give different and complementing information. It appears particularly useful to employ a combination of active and passive methods because the use of active laser spectroscopy allows the obtaining of specific information on thermal infrared reflectance of surface materials. It seems to be evident that a spectrometric survey of Martian materials has to be focused on the analysis of altered and fresh mafic materials and rocks, water-bearing silicates, and possibly carbonates

XMM-Newton observation of the ULIRG NGC 6240: The physical nature of the complex Fe K line emission

We report on an XMM-Newton observation of the ultraluminous infrared galaxy NGC 6240. The 0.3-10 keV spectrum can be successfully modelled with: (i) three collisionally ionized plasma components with temperatures of about 0.7, 1.4, and 5.5 keV; (ii) a highly absorbed direct power-law component; and (iii) a neutral Fe K_alpha and K_beta line. We detect a significant neutral column density gradient which is correlated with the temperature of the three plasma components. Combining the XMM-Newton spectral model with the high spatial resolution Chandra image we find that the temperatures and the column densities increase towards the center. With high significance, the Fe K line complex is resolved into three distinct narrow lines: (i) the neutral Fe K_alpha line at 6.4 keV; (ii) an ionized line at about 6.7 keV; and (iii) a higher ionized line at 7.0 keV (a blend of the Fe XXVI and the Fe K_beta line). While the neutral Fe K line is most probably due to reflection from optically thick material, the Fe XXV and Fe XXVI emission arises from the highest temperature ionized plasma component. We have compared the plasma parameters of the ultraluminous infrared galaxy NGC 6240 with those found in the local starburst galaxy NGC 253. We find a striking similarity in the plasma temperatures and column density gradients, suggesting a similar underlying physical process at work in both galaxies.Comment: 8 pages including 9 figures. Accepted for publication in A&

Deep ROSAT Surveys & the contribution of AGNs to the soft X-ray background

The ROSAT Deep Surveys in the Lockman Hole have revealed that AGNs are the main contributors (~75%) to the soft X-ray background in the 1–2 keV band. Using new optical/infrared and radio observations we have obtained a nearly complete identification (93%) of the 91 X-ray sources down to a limiting flux of 1.2·10^(–15) erg cm^(–2) s^(–1) in the 0.5–2.0 keV band. We present the optical colors and the emission line properties of our AGNs in comparison with other X-ray selected AGN samples. Furthermore we discuss the fraction of red AGNs found in the ROSAT Deep Surveys. From the ROSAT Deep Surveys we see no evidence for a new class of X-ray bright galaxies, which significantly contributes to the soft X-ray background

Formation and evolution of clumpy tidal tails around globular clusters

We present some results of numerical simulations of a globular cluster orbiting in the central region of a triaxial galaxy on a set of 'loop' orbits. Tails start forming after about a quarter of the globular cluster orbital period and develop, in most cases, along the cluster orbit, showing clumpy substructures as observed, for example, in Palomar 5. If completely detectable, clumps can contain about 7,000 solar masses each, i.e. about 10% of the cluster mass at that epoch. The morphology of tails and clumps and the kinematical properties of stars in the tails are studied and compared with available observational data. Our finding is that the stellar velocity dispersion tends to level off at large radii, in agreement to that found for M15 and Omega Centauri.Comment: LaTeX 2e, uses AASTeX v5.x, 40 pages with 18 figures. Submitted to The Astronomical Journa

The contribution of Narrow-Line Seyfert 1 galaxies to the soft X-ray background

The ROSAT Ultradeep HRI survey in the Lockman Hole contains a complete sample of 91 X-ray sources with fluxes in the 0.5-2 keV band larger than 1.2 times 10e-15 erg cm-2 s-1, where over about 75 per cent of the sources are quasars or Seyfert galaxies. During the course of our optical identification work, we have obtained optical spectra of 67 narrow emission line galaxies (NELG), which are physically not associated with the X-ray sources. We have derived the equivalent width (EW) and the full width at half maximum (FWHM) for the most prominent emission lines of 41 quasars and Seyfert galaxies taken from the ROSAT Deep Survey (RDS), which has a flux limit of 5.5 times 10e-15 erg cm-2 s-1 in the 0.5-2.0 keV band. Furthermore we have obtained the EW and FWHM values of the field NELGs. Here we present the spectroscopic discrimination between RDS Seyfert galaxies and field galaxies (NELG). The analysis of the emission lines has revealed that a single object out of 69 spectroscopically identified AGN fits the optical criteria of Narrow-Line Seyfert 1 galaxies (NLS1). This may indicate that NLS1 contribute only marginally to the soft X-ray background, but we can not exclude a possible larger contribution.Comment: Invited talk presented at the Joint MPE,AIP,ESO workshop on NLS1s, Bad Honnef, Dec. 1999, to appear in New Astronomy Reviews; also available at http://wave.xray.mpe.mpg.de/conferences/nls1-worksho