An oxidorhenium(v) complex with an electron-withdrawing ligand: benefits and drawbacks for a dual role catalyst.

One very unique feature of oxidorhenium(v) complexes is their dual catalytic activity in both reduction of stable oxyanions like perchlorate ClO and nitrate NO as well as epoxidation of olefins. In our ongoing research efforts, we were interested to study how an electron-withdrawing ligand would affect both these catalytic reactions. Hence, we synthesized the novel bidentate dimethyloxazoline-dichlorophenol ligand HL1 and synthesized oxidorhenium(v) complex [ReOCl(L1)] (1).

Building towards an adolescent neural urbanome: Expanding environmental measures using linked external data (LED) in the ABCD study.

Many recent studies have demonstrated that environmental contexts, both social and physical, have an important impact on child and adolescent neural and behavioral development. The adoption of geospatial methods, such as in the Adolescent Brain Cognitive Development (ABCD) Study, has facilitated the exploration of many environmental contexts surrounding participants' residential locations without creating additional burdens for research participants (i.e.

Environmental inequality and disparities in school readiness: The role of neurotoxic lead.

Developmental science has increasingly scrutinized how environmental hazards influence child outcomes, but few studies examine how contaminants affect disparities in early skill formation. Linking research on environmental inequality and early childhood development, this study assessed whether differences in exposure to neurotoxic lead explain sociodemographic gaps in school readiness. Using panel data tracking a representative sample of 1266 Chicago children (50% female, 16% White, 30% Black, 49% Hispanic, μ  = 5.

Toxic Neighborhoods: The Effects of Concentrated Poverty and Environmental Lead Contamination on Early Childhood Development.

Although socioeconomic disparities in cognitive ability emerge early in the life course, most research on the consequences of living in a disadvantaged neighborhood has focused on school-age children or adolescents. In this study, we outline and test a theoretical model of neighborhood effects on cognitive development during early childhood that highlights the mediating role of exposure to neurotoxic lead. To evaluate this model, we follow 1,266 children in Chicago from birth through school entry and track both their areal risk of lead exposure and their neighborhoods' socioeconomic composition over time.

Parental Depression and Contextual Selection: The Case of School Choice.

Parental depression constricts children's development, but the mechanisms implicated-beyond daily parenting tactics-remain unknown. Today, parents must evaluate and select environmental contexts for child-rearing within increasingly complex residential and educational markets. Depression may hamper parents' abilities to navigate this terrain, constraining information collection and impairing child-oriented decision-making.

Vapochromism and Magnetochemical Switching of a Nickel(II) Paddlewheel Complex by Reversible NH Uptake and Release.

Reaction of [NiCl (PnH) ] (1) (PnH=6-tert-butyl-pyridazine-3-thione) with NiCl affords the binuclear paddlewheel (PW) complex [Ni (Pn) ] (2). Diamagnetic complex 2 is the first example of a PW complex capable of reversibly binding and releasing NH . The NH ligand in [Ni (Pn) (NH )] (2⋅NH ) enforces major spectroscopic and magnetic susceptibility changes, thus displaying vapochromic properties (λ (2)=532 nm, λ (2⋅NH )=518 nm) and magnetochemical switching (2: S=0; 2⋅NH : S=1).

Isomers in chlorido and alkoxido-substituted oxidorhenium(v) complexes: effects on catalytic epoxidation activity.

The syntheses and characterizations of oxidorhenium(v) complexes trans-dichlorido [ReOCl2(PPh3)(L1a)] (trans-2a), cis-dichlorido [ReOCl2(PPh3)(L1b)] (cis-2b) and ethoxido-complex [ReO(OEt)(L1b)2] (4b), ligated with the dimethyloxazoline-phenol ligands HL1a and HL1b are described. The bidentate ligand HL1a (2-(4,4-dimethyl-4,5-dihydro-1,3-oxazol-2-yl)-phenol) is unsubstituted on the phenol ring; ligand HL1b (2-(4,4-dimethyl-4,5-dihydro-1,3-oxazol-2-yl)-4-nitrophenol) contains a nitro group in para-position to the hydroxy group. In the reaction of precursor complex [ReOCl3(PPh3)2] and HL1a the two stereoisomers cis/trans-2a, with respect to chlorido ligands, are formed.

Skill-Based Contextual Sorting: How Parental Cognition and Residential Mobility Produce Unequal Environments for Children.

Highly skilled parents deploy distinct strategies to cultivate their children's development, but little is known about how parental cognitive skills interact with metropolitan opportunity structures and residential mobility to shape a major domain of inequality in children's lives: the neighborhood. We integrate multiple literatures to develop hypotheses on parental skill-based sorting by neighborhood socioeconomic status and public school test scores, which we test using an original follow-up of the Los Angeles Family and Neighborhood Survey. These data include more than a decade's worth of residential histories for households with children that are linked to census, geographic information system, and educational administrative data.

Dioxygen Activation with Molybdenum Complexes Bearing Amide-Functionalized Iminophenolate Ligands.

Two novel iminophenolate ligands with amidopropyl side chains ( and ) on the imine functionality have been synthesized in order to prepare dioxidomolybdenum(VI) complexes of the general structure [MoO] featuring pendant internal hydrogen bond donors. For reasons of comparison, a previously published complex featuring -butyl side chains () was included in the investigation. Three complexes (-) obtained using these ligands (-) were able to activate dioxygen in an in situ approach: The intermediate molybdenum(IV) species [MoO(PMe)] is first generated by treatment with an excess of PMe.

Stereoisomers and functional groups in oxidorhenium(v) complexes: effects on catalytic activity.

The syntheses of oxidorhenium(v) complexes [ReOCl(L1a-c)] (3a-c), equipped with the bidentate, mono-anionic phenol-dimethyloxazoline ligands HL1a-c are described. Ligands HL1b-c contain functional groups on the phenol ring, compared to parent ligand 2-(4,4-dimethyl-4,5-dihydro-1,3-oxazol-2-yl)-phenol H1a; namely a methoxy group ortho to the hydroxyl position (2-(4,4-dimethyl-4,5-dihydro-1,3-oxazol-2-yl)-6-methoxyphenol, H1b), or a nitro group para to the hydroxyl position (2-(4,4-dimethyl-4,5-dihydro-1,3-oxazol-2-yl)-4-nitrophenol, H1c). Furthermore, oxidorhenate(v) complexes (NBu)[ReOCl(L1a-b)] (2a-b) were synthesized for solid state structural comparisons to 3a-b.

Iron catalyzed oxidation of benzylic alcohols to benzoic acids.

The bidentate N,O-ligands phenol-pyrazole (HL1), naphthol-pyrazole (HL2) and the commercially available ligand 5-methylphenol-benzotriazole (HL3) were used for the synthesis of novel iron(iii) complexes. The mononuclear iron complexes [FeCl(L1)2] (1), [FeCl(L2)2] (2) and [FeCl(L3)2] (3) are stable to air and moisture, both in the solid state as well as in solution, while the dinuclear, μ-oxido bridged complex [{Fe(L1)2}2(μ-O)] (1a) is air sensitive. All four complexes 1, 2, 3 and 1a were investigated for their catalytic activity in the direct one-pot oxidation of primary alcohols to carbonic acids with 30% aq.

WEALTH INEQUALITY AND ACCUMULATION.

Research on wealth inequality and accumulation and the data upon which it relies have expanded substantially in the twenty-first century. While the field has experienced rapid growth, conceptual and methodological challenges remain. We begin by discussing two major unresolved methodological concerns facing wealth research: how to address challenges to causal inference posed by wealth's cumulative nature and how to operationalize net worth, given its highly skewed nature.

Unusual C-N Coupling Reactivity of Thiopyridazines: Efficient Synthesis of Iron Diorganotrisulfide Complexes.

The reaction of iron(II) triflate with 6-tert-butyl-3-thiopyridazine (PnH) and 4-methyl-6-tert-butyl-3-thiopyridazine (PnH) respectively led to iron bis(diorganotrisulfide) complexes [Fe(PnSPn)](OTf) [R = H (1a) and Me (2a)]. The corresponding perchlorate complexes were prepared by using the iron(II) chloride precursor and the subsequent addition of 2 equiv of NaClO, giving [Fe(PnSPn)](ClO) [R = H (1b) and Me (2b)]. The compounds were fully characterized including single-crystal X-ray diffraction analysis.

Oxidorhenium(V) Complexes with Tetradentate Iminophenolate Ligands: Influence of Ligand Flexibility on the Coordination Motif and Oxygen-Atom-Transfer Activity.

The synthesis of oxidorhenium(V) complexes 1-3 coordinated by tetradentate iminophenolate ligands H2L1-H2L3 bearing backbones of different rigidity (alkyl, cycloalkyl, and phenyl bridges) allows for the formation of distinct geometric isomers, including a symmetric trans-oxidochlorido coordination motif in complex 3. The complex employing a cycloalkyl-bridged ligand (2) of intermediate rigidity exhibits an interesting solvent- and temperature-dependent equilibrium between a symmetric (trans) isomer and an asymmetric (cis) isomer in solution. The occurrence of a symmetric isomer for 2 and 3 is confirmed by single-crystal X-ray diffraction analysis.

Templated C-C and C-N Bond Formation Facilitated by a Molybdenum(VI) Metal Center.

Preparation of molybdenum dioxido complexes with novel iminophenolate ligands bearing pendant secondary amide functionalities led to unprecedented C-C and C-N coupling reactions of two α-iminoamides upon coordination. The diastereoselective cyclization to asymmetric imidazolidines occurs at the metal center in two consecutive steps via a monocoupled intermediate. A meaningful mechanism is proposed on the basis of full characterization of intermediate and final molybdenum-containing products by spectroscopic means and by single-crystal X-ray diffraction analyses.

Oxorhenium(V) complexes with phenolate-pyrazole ligands for olefin epoxidation using hydrogen peroxide.

Oxorhenium(V) complexes of the general formula [ReOCl2(PPh3)(L)] (2a-c) and [ReOCl(L)2] (3a-c) with L being monoanionic, bidentate phenolate-pyrazole ligands 1a-c that bear substituents with various electronic features on the phenol ring (1a Br, 1b NO2, 1c OMe) were prepared. The compounds are stable toward moisture and air, allowing them to be handled in a normal lab atmosphere. All complexes were fully characterized by spectroscopic means and, in the case of 2b, 2c, 3b, and 3c, also by single-crystal X-ray diffraction analyses.

Oxorhenium(V) complexes with phenolate-oxazoline ligands: influence of the isomeric form on the O-atom-transfer reactivity.

The bidentate phenolate-oxazoline ligands 2-(2'-hydroxyphenyl)-2-oxazoline (1a, Hoz) and 2-(4',4'-dimethyl-3',4'-dihydrooxazol-2'-yl)phenol (1b, Hdmoz) were used to synthesize two sets of oxorhenium(V) complexes, namely, [ReOCl2(L)(PPh3)] [L = oz (2a) and dmoz (2b)] and [ReOX(L)2] [X = Cl, L = oz (3a or 3a'); X = Cl, L = dmoz (3b); X = OMe, L = dmoz (4)]. Complex 3a' is a coordination isomer (N,N-cis isomer) with respect to the orientation of the phenolate-oxazoline ligands of the previously published complex 3a (N,N-trans isomer). The reaction of 3a' with silver triflate in acetonitrile led to the cationic compound [ReO(oz)2(NCCH3)](OTf) ([3a'](OTf)).

Oxorhenium(V) complexes of quinoline and isoquinoline carboxylic acids--synthesis, structural characterization and catalytic application in epoxidation reactions.

Six novel oxorhenium(V) complexes incorporating quinoline and isoquinoline carboxylic acid derivatives were prepared in good yields. Relying on the experimental conditions, compounds with two chelate ligands [ReOCl(iqc)2]·MeOH (1), [ReO(OMe)(iqc)2] (2), [ReO(OMe)(mqc)2] (3) and [ReO(OMe)(8-qc)2] (4) and compounds incorporating one bidentate ligand [ReOCl2(iqc)(PPh3)] (5) and [ReOCl2(mqc)(PPh3)] (6) were synthesized (iqcH = isoquinoline-1-carboxylic acid, mqcH = 4-methoxy-2-quinolinecarboxylic acid and 8-qcH = 8-quinolinecarboxylic acid). The reported compounds were characterized by spectroscopic methods and single crystal X-ray diffraction analysis.

Dioxomolybdenum(VI) complexes with pyrazole based aryloxide ligands: synthesis, characterization and application in epoxidation of olefins.

Synthesis, characterization, and epoxidation chemistry of four new dioxomolybdenum(VI) complexes [MoO(2)(L)(2)] (1-4) with aryloxide-pyrazole ligands L = L1-L4 is described. Catalysts 1-4 are air and moisture stable and easy to synthesize in only three steps in good yields. All four complexes are coordinated by the two bidentate ligands in an asymmetric fashion with one phenoxide and one pyrazole being trans to oxo atoms, respectively.

Unsymmetrical Ru-NHC catalysts: a key for the selective tandem ring opening-ring closing alkene metathesis (RO-RCM) of cyclooctene.

Dissymmetry for selectivity: NHC ligand with two different pendant group allows the selective formation of cyclic oligomers in place of polymers opening new strategy to generate macrocycles.

Oxorhenium(V) complexes with pyrazole based aryloxide ligands and application in olefin epoxidation.

We synthesized and characterized a set of new oxorhenium(V) complexes coordinated by various pyrazole containing phenol (L1-L3) and naphthol ligands (L4-L7). Depending on the starting material, we were able to selectively synthesize monosubstituded or disubstituted complexes of the type [ReOBr(2)L(PPh(3))] (1-7; L = L1-L7) and [ReOClL(2)] (L = L1 8; L2 9; L4 10; L6 11), respectively. All complexes are stable to air and moisture, both in solid state as well as in solution.

Synthesis and characterization of aluminum- and gallium-bridged [1.1]chromarenophanes and [1.1]molybdarenophanes.

The synthesis and structural characterization of the first [1.1]chromarenophanes and the first [1.1]molybdarenophanes are described.

The galla[1]ferrocenophane {[dimeth-yl(2-pyrid-yl)sil-yl]bis-(trimethyl-silyl)methyl-κC,N}(ferrocene-1,1'-di-yl)gallium(III).

The title compound, [GaFe(C(5)H(4))(2)(C(14)H(28)NSi(3))] or [{(2-H(4)C(5)N)Me(2)Si}(Me(3)Si)(2)C]Ga(C(5)H(4))(2)Fe, a galla[1]ferrocenophane, crystallizes with two independent mol-ecules in the asymmetric unit. In these strained sandwich compounds, the angles between the planes of the two π-ligands are 15.4 (2) and 16.

[1]molybdarenophanes: strained metallarenophanes with aluminum, gallium, and silicon in bridging positions.

The first [1]molybdarenophanes were synthesized and structurally characterized. The aluminum and gallium compounds [(Me2Ntsi)Al(eta6-C6H5)2Mo] (2a) and [(Me2Ntsi)Ga(eta6-C6H5)2Mo] (2b) [Me2Ntsi = C(SiMe3)2(SiMe2NMe2)] were obtained from [Mo(LiC6H5)2].TMEDA and (Me2Ntsi)ECl2 [E = Al, Ga] in analytical pure form with isolated yields of 74% (2a) and 52% (2b).