Heterobimetallic Complexes of Rhenium and Zinc: Potential Catalysts for Homogeneous Syngas Conversion

6-(Diphenylphosphino)-2,2′-bipyridine (PNN) coordinates to rhenium carbonyls in both κ^1(P) and κ^2(N,N) modes; in the former, the free bpy moiety readily binds to zinc alkyls and halides. [Re(κ^1(P)-PNN)(CO)_5][OTf] reacts with dialkylzinc reagents to form [Re(κ^1(P)-PNN·ZnR)(CO)_4(μ_(2-)C(O)R)][OTf] (R = Me, Et, Bn), in which an alkyl group has been transferred to a carbonyl carbon and the resulting monoalkyl Zn is bound both to the bpy nitrogens and the acyl oxygen. ZnCl_2 binds readily to the bpy group in Re(κ^1(P)-PNN)(CO)_4Me, and the resulting adduct undergoes facile migratory insertion, assisted by the Lewis acidic pendent Zn, to yield Re(κ^1(P)-PNN·ZnCl)(μ_(2-)Cl)(CO)_3(μ_(2-)C(O)Me), in which one of the chlorides occupies the sixth coordination site on Re. Migratory insertion is inhibited by THF or other ethers that can coordinate to ZnCl_2. Migratory insertion is also observed for Re(κ1(P)-PNN)(CO)_4(CH_2Ph) but not for Re(κ^1(P)-PNN)(CO)_4(CH_2OCH_3); coordination of the methoxy oxygen to Zn appears to block its ability to coordinate to the carbonyl oxygen and facilitate migratory insertion. Intramolecular Lewis acid promoted hydride transfer from [(dmpe)_2PtH][PF_6] to a carbonyl in [Re(κ^1(P)-PNN)(CO)_5][OTf] results in formation of a Re–formyl species; additional hydride transfer leads to a novel Re–Zn-bonded product along with some formal dehyde

Transformations of Group 7 Carbonyl Complexes: Possible Intermediates in a Homogeneous Syngas Conversion Scheme

A variety of C−H and C−C bond forming reactions of group 7 carbonyl complexes have been studied as potential steps in a homogeneously catalyzed conversion of syngas to C_(2+) compounds. The metal formyl complexes M(CO)_3(PPh_3)_2(CHO) (M = Mn, Re) are substantially stabilized by coordination of boranes BX_3 (X = F, C_6F_5) in the form of novel boroxycarbene complexes M(CO)_3(PPh_3)_2(CHOBX_3), but these boron-stabilized carbenes do not react with hydride sources to undergo further reduction to metal alkyls. The related manganese methoxycarbene cations [Mn(CO)_(5−x)(PPh_3)_x(CHOMe)]+ (x = 1 or 2), obtained by methylation of the formyls, do react with hydrides to form methoxymethyl complexes, which undergo further migratory insertion under an atmosphere of CO. The resulting acyls, cis- and trans-Mn(PPh_3)(CO)_4(C(O)CH_2OMe), can be alkylated to form the cationic carbene complex [Mn(PPh_3)(CO)_4(C(OR)CH_2OMe)]^+, which undergoes a 1,2 hydride shift to form 1,2-dialkoxyethylene, which is displaced from the metal, releasing triflate or diethyl ether adducts of [Mn(PPh_3)(CO)_4]^+. The acyl can also be protonated with HOTf to form a hydroxycarbene complex, which rearranges to Mn(PPh_3)(CO)_4(CH_2COOMe) and is protonolyzed to yield methyl acetate and [Mn(PPh_3)(CO)_4]^+; addition of L (L = PPh_3, CO) to the manganese cation regenerates [Mn(PPh_3)(CO)_4(L)]^+. Since the original formyl complex can be obtained by the reaction of [Mn(PPh_3)(CO)_5]^+ with [PtH(dmpe)_2]^+, which in turn can be generated from H_2, this set of transformations amounts to a stoichiometric cycle for selectively converting H_2 and CO into a C_2 compound under mild conditions

Hunting The Most Distant Stars in the Milky Way: Methods and Initial Results

We present a new catalog of 404 M giant candidates found in the UKIRT Infrared Deep Sky Survey (UKIDSS). The 2,400 deg$^2$ available in the UKIDSS Large Area Survey Data Release 8 resolve M giants through a volume four times larger than that of the entire Two Micron All Sky Survey. Combining near-infrared photometry with optical photometry and proper motions from the Sloan Digital Sky Survey yields an M giant candidate catalog with less M dwarf and quasar contamination than previous searches for similarly distant M giants. Extensive follow-up spectroscopy of this sample will yield the first map of our Galaxy's outermost reaches over a large area of sky. Our initial spectroscopic follow-up of $\sim$ 30 bright candidates yielded the positive identification of five M giants at distances $\sim 20-90$ kpc. Each of these confirmed M giants have positions and velocities consistent with the Sagittarius stream. The fainter M giant candidates in our sample have estimated photometric distances $\sim 200$ kpc (assuming $[Fe/H]$ = 0.0), but require further spectroscopic verification. The photometric distance estimates extend beyond the Milky Way's virial radius, and increase by $\sim 50\%$ for each 0.5 dex decrease in assumed $[Fe/H]$. Given the number of M giant candidates, initial selection efficiency, and volume surveyed, we loosely estimate that at least one additional Sagittarius-like accretion event could have contributed to the hierarchical build-up of the Milky Way's outer halo.Comment: 16 pages, 11 figures, emulateapj format. Accepted by A

The ACS Virgo Cluster Survey XV. The Formation Efficiencies of Globular Clusters in Early-Type Galaxies: The Effects of Mass and Environment

The fraction of stellar mass contained in globular clusters (GCs), also measured by number as the specific frequency, is a fundamental quantity that reflects both a galaxy's early star formation and its entire merging history. We present specific frequencies, luminosities, and mass fractions for the globular cluster systems of 100 early-type galaxies in the ACS Virgo Cluster Survey, the largest homogeneous catalog of its kind. We find that 1) GC mass fractions can be high in both giants and dwarfs, but are universally low in galaxies with intermediate luminosities. 2) The behavior of specific frequency across galaxy mass is dominated by the blue GCs. 3) The GC fractions of low-mass galaxies exhibit a dependence on environment. Nearly all dwarf galaxies with high GC fractions are within 1 Mpc of the cD galaxy M87, presenting the first strong evidence that GC formation in dwarfs is biased toward dense environments. 4) GC formation in central dwarfs is biased because their stars form earliest and most intensely. Comparisons to the Millennium Simulation show that central dwarfs have older stellar populations and form more stars at higher star formation rates (SFRs) and SFR surface densities. The SFR surface density in simulated dwarfs peaks before the total SFR, naturally producing GC populations that are older and more metal-poor than the field stars. 5) Dwarfs within ~40 kpc of the giant ellipticals M87 and M49 are red and have few or no GCs, suggesting that they have been tidally stripped and have contributed their GCs to the halos of their giant neighbors. The central dwarfs with high GC mass fractions are thus likely to be the survivors most similar to the protogalaxies that assembled the rich M87 globular cluster system.(Abridged)Comment: 27 pages, 21 figures, 7 tables. Accepted for publication in the Astrophysical Journa

Preimplantation chromosomal mosaics, chimaeras and confined placental mosaicism

Some human preimplantation embryos are chromosomally mosaic. For technical reasons, estimates of the overall frequency vary widely from 90% and the true frequency remains unknown. Aneuploid/diploid and aneuploid/aneuploid mosaics typically arise during early cleavage stages before the embryonic genome is fully activated and when cell cycle checkpoints are not operating normally. Other mosaics include chaotic aneuploid mosaics and mixoploids, some of which arise by abnormal chromosome segregation at the first cleavage division. Chimaeras are similar to mosaics, in having two genetically distinct cell populations, but they arise from more than one zygote and occur less often. After implantation, the frequency of mosaic embryos declines to about 2% and most are trisomic/diploid mosaics, with trisomic cells confined to the placenta. Thus, few babies are born with chromosomal mosaicism. This review discusses the origin of different types of chromosomal mosaics and chimaeras; their fate and the relationship between preimplantation chromosomal mosaicism and confined placental mosaicism in human conceptuses and animal models. Abnormal cells in mosaic embryos may be depleted by cell death, other types of cell selection or cell correction but the most severely affected mosaic embryos probably die. Trisomic cells could become restricted to placental lineages if cell selection or correction is less effective in placental lineages and/or they are preferentially allocated to a placental lineage. However, the relationship between preimplantation mosaicism and confined placental mosaicism may be complex because the specific chromosome(s) involved will influence whether chromosomally abnormal cells survive predominately in the placental trophoblast and/or placental mesenchyme. LAY SUMMARY: Human cells normally have 23 pairs of chromosomes, which carry the genes. During the first few days of development, some human embryos are chromosomal mosaics. These mosaic embryos have both normal cells and cells with an abnormal number of chromosomes, which arise from the same fertilised egg. (More rarely, the different cell populations arise from more than one fertilised egg and these embryos are called chimaeras.) If chromosomally abnormal cells survive to term, they could cause birth defects. However, few abnormal cells survive and those that do are usually confined to the placenta, where they are less likely to cause harm. It is not yet understood how this restriction occurs but the type of chromosomal abnormality influences which placental tissues are affected. This review discusses the origin of different types of chromosomally abnormal cells, their fate and how they might become confined to the placenta in humans and animal models

The ACS Fornax Cluster Survey. II. The Central Brightness Profiles of Early-Type Galaxies: A Characteristic Radius on Nuclear Scales and the Transition from Central Luminosity Deficit to Excess

We analyse HST surface brightness profiles for 143 early-type galaxies in the Virgo and Fornax Clusters. Sersic models provide accurate descriptions of the global profiles with a notable exception: the observed profiles deviate systematically inside a characteristic "break" radius of R_b ~ 0.02R_e where R_e is the effective radius of the galaxy. The sense of the deviation is such that bright galaxies (M_B < -20) typically show central light deficits with respect to the inward extrapolation of the Sersic model, while the great majority of low- and intermediate-luminosity galaxies (-19.5 < M_B < -15) show central light excesses; galaxies occupying a narrow range of intermediate luminosities (-20 < M_B < -19.5) are usually well fitted by Sersic models over all radii. The slopes of the central surface brightness profiles, when measured at fixed fractions of R_e, vary smoothly as a function of galaxy luminosity in a manner that depends sensitively on the choice of measurement radius. We show that a recent claim of strong bimodality in slope is likely an artifact of the galaxy selection function used in that study. To provide a more robust characterization of the inner regions of galaxies, we introduce a parameter that describes the central luminosity deficit or excess relative to the inward extrapolation of the outer Sersic model. We find that this parameter varies smoothly over the range of ~ 720 in blue luminosity spanned by the Virgo and Fornax sample galaxies, with no evidence for a dichotomy. We argue that the central light excesses (nuclei) in M_B > -19 galaxies may be the analogs of the dense central cores that are predicted by some numerical simulations to form via gas inflows. (ABRIDGED)Comment: To appear in the Astrophysical Journal, December 2007. Full resolution paper available at http://www.cfa.harvard.edu/~ajordan/ACSFCS/Home.htm

The Most Distant Stars in the Milky Way

We report on the discovery of the most distant Milky Way (MW) stars known to date: ULAS J001535.72$+$015549.6 and ULAS J074417.48$+$253233.0. These stars were selected as M giant candidates based on their infrared and optical colors and lack of proper motions. We spectroscopically confirmed them as outer halo giants using the MMT/Red Channel spectrograph. Both stars have large estimated distances, with ULAS J001535.72$+$015549.6 at $274 \pm 74$ kpc and ULAS J074417.48$+$253233.0 at 238 $\pm$ 64 kpc, making them the first MW stars discovered beyond 200 kpc. ULAS J001535.72$+$015549.6 and ULAS J074417.48$+$253233.0 are both moving away from the Galactic center at $52 \pm 10$ km s$^{-1}$ and $24 \pm 10$ km s$^{-1}$, respectively. Using their distances and kinematics, we considered possible origins such as: tidal stripping from a dwarf galaxy, ejection from the MW's disk, or membership in an undetected dwarf galaxy. These M giants, along with two inner halo giants that were also confirmed during this campaign, are the first to map largely unexplored regions of our Galaxy's outer halo.Comment: Accepted and in print by ApJL. Seven pages, 2 figure