Silacalix-

The synthesis of polyphosphinine macrocycles, which consist of a 16-membered ring with four phosphorus atoms (P4) and a 12-membered ring with three phosphorus atoms (P3), is described. Their high coordination ability is demonstrated by the quantitative synthesis of the rhodium and iridium cation complexes of the P4 macrocycle and by quantitative synthesis of the W(CO)3 complex of the P3 compound. Unlike the other available macrocyclic ligands bearing oxygen, sulfur, di- or tricoordinate nitrogen, and even tricoordinate phosphorus as ligating atoms, which are all essentially final sigma donors, these dicoordinate phosphorus-based macrocycles have strong pi-acceptor properties. Their use can be envisaged for the stabilization of negative oxidation states of transition metals or in reductive catalysis.     

Catalysis by transition metals: metal-carbon double and triple bonds

Several well-characterized transition metal catalysts contain a metal-carbon double bond or a metal-carbon triple bond. In other homogeneous (or heterogeneous) catalyst systems in which the metal is likely to be in a relatively high oxidation state, such as molybdenum(VI) or tungsten(VI), metal-carbon multiple bonds may play an important role. Some recent results suggest that even supposedly well understood reactions such as ethylene polymerization may actually involve catalysts that behave as if they contained a metal-carbon double bond instead of a metal-carbon single bond. The chemistry of metal-carbon double and triple bonds should eventually complement and perhaps. overlap the known chemistry of complexes containing metal-oxygen double bonds or metal-nitrogen triple bonds, respectively; unique catalytic reactions involving carbon, nitrogen, and oxygen ligands multiply bonded to transition metals are therefore possible.     

Electron localization determines defect formation on ceria substrates

The high performance of ceria (CeO2) as an oxygen buffer and active support for noble metals in catalysis relies on an efficient supply of lattice oxygen at reaction sites governed by oxygen vacancy formation. We used high-resolution scanning tunneling microscopy and density functional calculations to unravel the local structure of surface and subsurface oxygen vacancies on the (111) surface. Electrons left behind by released oxygen localize on cerium ions. Clusters of more than two vacancies exclusively expose these reduced cerium ions, primarily by including subsurface vacancies, which therefore play a crucial role in the process of vacancy cluster formation. These results have implications for our understanding of oxidation processes on reducible rare-earth oxides.     

Deep UV photochemistry of chemisorbed monolayers: patterned coplanar molecular assemblies

Deep ultraviolet (UV) irradiation is shown to modify organosilane self-assembled monolayer (SAM) films by a photocleavage mechanism, which renders the surface amenable to further SAM modification. Patterned UV exposure creates alternating regions of intact SAM film and hydrophilic, reactive sites. The exposed regions can undergo a second chemisorption reaction to produce an assembly of SAMs in the same molecular plane with similar substrate attachment chemistry. The UV-patterned films are used as a template for selective buildup of fluorophores, metals, and biological cells.     

Molecular octa-uranium rings with alternating nitride and azide bridges

Uranium nitrides offer potential as future nuclear fuels and as probes of metal ligand multiple bonding involving the f-block actinide metals. However, few molecular examples are available for study owing to the difficulties in synthesis. Recent advances in organoactinide chemistry have provided a route to uranium nitride complexes that expands the options for developing UN chemistry. Several 24-membered uranium nitrogen rings, (UNUN3)4, have been synthesized by reduction of sodium azide with organometallic metallocene derivatives, [(C5Me4R)2U][(mu-Ph)2BPh2] (R = Me, H; Me = methyl, Ph = phenyl). The nanometer-sized rings contain unusual UNU nitride linkages that have short U-N distances within the double-bond range.     

Nanophase transition metal oxides show large thermodynamically driven shifts in oxidation-reduction equilibria

Knowing the thermodynamic stability of transition metal oxide nanoparticles is important for understanding and controlling their role in a variety of industrial and environmental systems. Using calorimetric data on surface energies for cobalt, iron, manganese, and nickel oxide systems, we show that surface energy strongly influences their redox equilibria and phase stability. Spinels (M(3)O(4)) commonly have lower surface energies than metals (M), rocksalt oxides (MO), and trivalent oxides (M(2)O(3)) of the same metal; thus, the contraction of the stability field of the divalent oxide and expansion of the spinel field appear to be general phenomena. Using tabulated thermodynamic data for bulk phases to calculate redox phase equilibria at the nanoscale can lead to errors of several orders of magnitude in oxygen fugacity and of 100 to 200 kelvin in temperature.     

Polymer synthesis and organotransition metal chemistry

Mechanistic and synthetic studies in organometallic chemistry have provided considerable insight into olefin metathesis and Ziegler-Natta polymerization. New homogeneous olefin metathesis catalysts based on high oxidation state transition metals have opened new opportunities in polymer synthesis by providing unprecedented control in ring-opening polymerization of cyclic alkenes. The recent development of living coordinative polymerization systems has led to the preparation of a number of new, interesting materials, including block copolymers, conducting polymers or precursors, and ionophoric polymeric substrates.     

Atomic-scale structure and catalytic reactivity of the RuO(2)(110) surface

The structure of RuO(2)(110) and the mechanism for catalytic carbon monoxide oxidation on this surface were studied by low-energy electron diffraction, scanning tunneling microscopy, and density-functional calculations. The RuO(2)(110) surface exposes bridging oxygen atoms and ruthenium atoms not capped by oxygen. The latter act as coordinatively unsaturated sites-a hypothesis introduced long ago to account for the catalytic activity of oxide surfaces-onto which carbon monoxide can chemisorb and from where it can react with neighboring lattice-oxygen to carbon dioxide. Under steady-state conditions, the consumed lattice-oxygen is continuously restored by oxygen uptake from the gas phase. The results provide atomic-scale verification of a general mechanism originally proposed by Mars and van Krevelen in 1954 and are likely to be of general relevance for the mechanism of catalytic reactions at oxide surfaces.     

Dissociation of individual molecules with electrons from the tip of a scanning tunneling microscope

The scanning tunneling microscope (STM) can be used to select a particular adsorbed molecule, probe its electronic structure, dissociate the molecule by using electrons from the STM tip, and then examine the dissociation products. These capabilities are demonstrated for decaborane(14) (B(10)H(14)) molecules adsorbed on a silicon(111)-(7 x 7) surface. In addition to basic studies, such selective dissociation processes can be used in a variety of applications to control surface chemistry on the molecular scale.     

A predictably selective aliphatic C-H oxidation reaction for complex molecule synthesis

Realizing the extraordinary potential of unactivated sp3 C-H bond oxidation in organic synthesis requires the discovery of catalysts that are both highly reactive and predictably selective. We report an iron (Fe)-based small molecule catalyst that uses hydrogen peroxide (H2O2) to oxidize a broad range of substrates. Predictable selectivity is achieved solely on the basis of the electronic and steric properties of the C-H bonds, without the need for directing groups. Additionally, carboxylate directing groups may be used to furnish five-membered ring lactone products. We demonstrate that these three modes of selectivity enable the predictable oxidation of complex natural products and their derivatives at specific C-H bonds with preparatively useful yields. This type of general and predictable reactivity stands to enable aliphatic C-H oxidation as a method for streamlining complex molecule synthesis.     

Electron transfer-induced dynamics of oxygen molecules on the TiO2(110) surface

Diffusion of oxygen molecules on transition metal oxide surfaces plays a vital role for the understanding of catalysis and photocatalysis on these materials. By means of time-resolved scanning tunneling microscopy, we provide evidence for a charge transfer-induced diffusion mechanism for O2 molecules adsorbed on a rutile TiO2(110) surface. The O2 hopping rate depended on the number of surface donors (oxygen vacancies), which determines the density of conduction band electrons. These results may have implications for the understanding of oxidation processes on metal oxides in general.     

Molecular recognition and metal ion template synthesis

Methods for the design and synthesis of ligands intended to be specific for a metal ion have been a recent chemical development. This article describes how this process can be inverted so that the specifics of the coordination environment around the metal ion can be used as a template in large-scale ligand synthesis. The synthesis of macrobicyclic ligands for ferric ion has been accomplished by using active esters of catechol ligands in which catecholate coordination to iron is a prelude to the organic chemical reactions that link the coordination subunits together into one ligand system surrounding a central metal ion coordination site. The lanthanide(III) ions, which are among the most labile metal ions known, have coordination numbers of 8 or higher, and thus their encapsulation into a macrobicyclic structure is a challenging problem. Lanthanide amine complexes have been used as metal templates in the synthesis of such macrobicyclic lanthanide complexes. There is evidence that such a complex is inert to exchange in aqueous solution.     

铁氧化物-硅酸盐复合物的形成、性质及其对砷的固定

铁氧化物与硅酸盐矿物是土壤中最重要、最活跃的固相组分,它们之间的交互作用直接影响土壤物理化学特性,可有效地调控土壤(类)重金属的迁移、转化。本文以铁氧化物和硅酸盐矿物胶结过程中的一些表观特征变化为出发点,从宏观、表观到微观综述了二者交互作用的界面特性和机理、交互作用前后对土壤砷的固定与释放机制等内容。本文阐明层状硅酸盐与铁氧化物通过多种化学作用而发生表面复合,其中静电作用是作用力之一,带负电荷的硅酸盐与带正电荷的铁氧化物在静电引力的作用下迅速结合,在胶体表面双电层上形成二元团聚体;形成的二元团聚体可改变土壤矿物的表面积和孔性结构、表面电化学特性和物理性质。同时,铁氧化物-硅酸盐复合物表面的活性基团可以通过内层络合共氧的方式将土壤中AsO_4~(2-)络合,形成单核或双核表面络合物而固定砷。复合物对AsO_4~(2-)的吸附能力介于铁氧化物和硅酸盐矿物之间,并更接近铁氧化物的表面吸附特性。本文旨在为土壤砷的原位固定提供理论支撑。     

Concentration of nitrite and nonthiol nitroso compounds in tissues as a high sensitive marker of leukocyte activity

This paper shows that the inflammation-induced appearance of nitrite and nonthiol nitroso compounds in the hen blood and cow milk is due to oxidation of dinitrosyl iron complexes (DNIC) and nitrosothiols (RSNO) by reactive oxygen species (ROS), which are produced by activated leukocytes. Since DNIC and RSNO are highly effective ROS scavengers, the content of nitrite and nonthiol nitroso compounds can be regarded as one of the most sensitive indicators of leukocyte activation.     

Organorhenium chemistry

As organometallic chemists have delved into the chemistry of rhenium, an amazing variety of unusual stable organorhenium compounds have been synthesized and novel reaction pathways have been uncovered. The broad range of stable organorhenium compounds can be traced to the availability of oxidation states from -III to VII and to the high strength of bonds to rhenium. New types of reaction mechanism are seen in response to the reluctance of rhenium to form coordinatively unsaturated complexes.     

Reactivity of the gold/water interface during selective oxidation catalysis

The selective oxidation of alcohols in aqueous phase over supported metal catalysts is facilitated by high-pH conditions. We have studied the mechanism of ethanol and glycerol oxidation to acids over various supported gold and platinum catalysts. Labeling experiments with (18)O(2) and H(2)(18)O demonstrate that oxygen atoms originating from hydroxide ions instead of molecular oxygen are incorporated into the alcohol during the oxidation reaction. Density functional theory calculations suggest that the reaction path involves both solution-mediated and metal-catalyzed elementary steps. Molecular oxygen is proposed to participate in the catalytic cycle not by dissociation to atomic oxygen but by regenerating hydroxide ions formed via the catalytic decomposition of a peroxide intermediate.     

Stable magnesium(I) compounds with Mg-Mg bonds

The chemistry of the group 2 metals (beryllium, magnesium, calcium, strontium, and barium) is dominated by the +2 oxidation state. Here, we report the reductions of two magnesium(II) iodide complexes with potassium metal in toluene, leading to thermally stable magnesium(I) compounds, (L)MgMg(L) (where L is [(Ar)NC(NPri2)N(Ar)]- or {[(Ar)NC(Me)]2CH}-, Ar is 2,6-diisopropylphenyl, Me is methyl, and Pri is isopropyl) in moderate yields. The results of x-ray crystallographic and theoretical studies are consistent with central Mg2+(2) units that have single, covalent magnesium-magnesium bonding interactions with 2.8508 +/- 0.0012 (standard deviation) and 2.8457 +/- 0.0008 angstrom bond lengths, respectively, and predominantly ionic interactions with the anionic ligands (L).     

Ore metals through geologic history

The ores of chromite, nickel, copper, and zinc show a wide distribution over geologic time, but those of iron, titanium, lead, uranium, gold, silver, molybdenum, tungsten, and tin are more restricted. Many of the limitations to specific time intervals are probably imposed by the evolving tectonic history of Earth interacting with the effects of the biomass on the evolution of the earth's s surface chemistry. Photosynthetic generation of free oxygen and "carbon" contributes significantlly to the diversity of redox potentials in both sedimentary and igneous-related processes of ore formation, influencing the selection of metals at the source, during transport, and at the site of ore deposition.     

Heterogeneous catalysis: some recent developments

In recent years major progress has been made in the area of heterogeneous catalysis by metals. Much has been learned about the nature of metal catalysts and of catalytic phenomena on metals. Characteristic patterns of catalytic behavior among the metallic elements have been established for certain classes of reactions, and these patterns provide a first step toward a more comprehensive understanding of catalytic specificity. Studies on metal alloys and related bimetallic catalysts have revived interest in a geometric factor in surface catalysis to complement the traditional electronic factor. Closely related to this geometric factor is the discovery that selectivity, rather than activity alone, is a major factor in reactions on bimetallic catalysts. Concurrent with progress in understanding how catalysts work, advances are also being made in the development of new catalyst systems, examples of which are the bimetallic (or polymetallic) cluster catalysts. Research in this area provides an example of how advances in catalyst technology can be realized within a framework of fundamental research on catalytic phenomena (38).     

植物根系限制重(类)金属吸收/转运的因素及其机制

当前土壤重(类)金属污染导致的农作物重(类)金属超标已成为我国居民严重关切的问题之一。在重(类)金属胁迫下,植物自身具备了相应的机制来减少其对重(类)金属的吸收富集,这些机制主要与土壤-植物根系系统中发生的一些物理、化学和生物学过程有关。本综述阐述了与植物根系相关的限制重(类)金属吸收/转运因素及其机制,主要包括:1)根系的一些分泌物能通过与重金属螯合降低其有效性,从而达到固定重金属的目的;2)在重(类)金属胁迫下,植物根系增加粗根比例,降低细根数量并减少根比表面积,从而降低与重(类)金属接触的几率并影响重(类)金属的吸收;3)水生植物根系表面形成氧化铁/锰化合物胶体,这些胶体能吸附阴阳离子,从而束缚重(类)金属;4)植物根系表面具有相应的吸附位点,具有相似性质的离子会对这些位点产生竞争,从而降低重(类)金属进入根系细胞的几率;5)细胞壁组分含有的基团可与重金属结合,从而束缚大量的重金属;6)植物根系内皮层凯氏带能阻断重(类)金属在皮层与维管柱之间的质外体运输,从而阻止重(类)金属向地上部分转运;7)具有相似性质的金属离子可对根系细胞膜上的离子通道展开竞争,这一过程影响重(类)金属的吸收;8)在细胞中游离的重(类)金属可被区隔到根系液泡中,从而减少其毒性以及向地上部分的转运;9)根系细胞膜上的一些基因的表达限制了重金属由根系向地上部分的转运。综上所述,植物主要通过减少根系与重(类)金属接触几率、吸附机制、离子竞争性吸收、以及区隔化作用等机制来降低重(类)金属的吸收和转运。但关于细胞壁组分在束缚阴离子形态存在类金属的相关机制还不清楚,尚待进一步明晰和阐明。