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Nucleophilic addition of organometallic reagents to carbonyl substrates constitutes one of the most fundamental operations in organic synthesis. Modification of the organometallic compounds by chiral, nonracemic auxiliaries offers a general opportunity to create optically active alcohols, and the catalytic version in particular provides maximum synthetic efficiency. The use of organozinc chemistry, unlike conventional organolithium or -magnesium chemistry, has realized an ideal catalytic enantioselective alkylation of aldehydes leading to a diverse array of secondary alcohols of high optical purity. A combination of dialkylzinc compounds and certain sterically constrained β-dialkylamino alcohols, such as (–)-3-exo-dimethylaminoiso- borneol [(–)-DAIB], as chiral inducers affords the best result (up to 99% ee). The alkyl transfer reaction occurs via a dinuclear Zn complex containing a chiral amino alkoxide, an aldehyde ligand, and three alkyl groups. The chiral multiplication method exhibits enormous chiral amplification: a high level of enantioselection (up to 98%) is attainable by use of DAIB in 14% ee. This unusual nonlinear effect is a result of a marked difference in chemical properties of the diastereomeric (homochiral and heterochiral) dinuclear complexes formed from the dialkylzinc and the DAIB auxiliary. This phenomenon may be the beginning of a new generation of enantioselective organic reactions. 相似文献
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M. Tsutsui M. Hancock J. Ariyoshi M. N. Levy 《Angewandte Chemie (International ed. in English)》1969,8(6):410-420
σ-Bonded organic groups in transition-metal complexes can rearrange to π-bonding ligands and vice versa: the classic example is the formation of π-arenechromium complexes from σ-arylchromium compounds. Rearrangements of this kind can be induced, inter alia, by reactions of the metal or of the ligand, as well as by migration or insertion of a ligand. Rearrangements play a role in many industrial processes, including the polymerization and isomerization of olefins and the hydroformylation of olefins. 相似文献
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Metal carbonyl clusters possess a complicated chemistry that is only beginning to be understood. One of the main current goals in this area is thus an understanding of their reactivity. This article describes the syntheses and reactions of clusters that contain metal carbonyl fragments bridged by a main-group element. But what is the sense of making such clusters still more complicated by the incorporation of main-group elements? The example of μ3-bridged carbonyl clusters will serve to show that the main-group element plays an important role in the study of reaction paths; it holds the metal carbonyl fragments together even when the bonds between them are broken in the course of a reaction. Trinuclear μ3-bridged clusters prove to be small enough to allow the analysis of typical cluster reactions (such as the reversible breaking of metal-metal bonds) in terms of single reaction steps. They are also large enough to provide surprises by their multifaceted reactivity. It will be shown that a detailed study of trinuclear RX-bridged metal carbonyl clusters (X ? N, P, As, Sb, Bi)—a very small part of carbonyl cluster chemistry—can lead to a better understanding of the general reaction principles involved. 相似文献
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Hans Wolfgang Kohlschütter 《Angewandte Chemie (International ed. in English)》1975,14(4):193-195
An interesting and topical question in modern inorganic chemistry is: To what extent are the well-known chemistry of dispersed metals and the new technique of chemical synthesis with free metal atoms interrelated? Or in other words: Where, do these two facets of metal chemistry meet? In an attempt to glean an answer to this question three important aspects are considered: metal sols, activated metals as powders, and deposits in vacuum processes (evaporation and cathodic sputtering of metals). 相似文献
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Joachim Wachter 《Angewandte Chemie (International ed. in English)》1989,28(12):1613-1626
Metal-sulfur centers play an important role in the activity of metalloproteins in enzymatic catalysis and the activity of metal sulfides as heterogeneous catalysts. The systematic search for M? S model compounds led to the discovery of an interesting and novel structural chemistry, which stems from the numerous coordination possibilities of sulfur ligands. The intention of this review article is to present and outline new approaches to sulfur chemistry from the organometallic point of view. Reactive cyclopentadienyl-transition metal fragments incorporate elemental sulfur to give polynuclear sulfur-rich complexes, which can contain either mono-, di- or polysulfido ligands or several such ligands in combined form. The versatile structural chemistry of the complexes formed and their reactivity towards organic, inorganic and organometallic compounds are discussed, and examples of some simple and rational procedures for their synthesis starting from cyclopentadienylcarbonyl- and cyclopentadienylhydrido-complexes are outlined. Their reactivity is manifested in numerous metal- and ligandcentered reactions. Finally the, albeit far less extensive, complex chemistry of the other chalcogens (O, Se, Te) is also considered for comparison, thus providing a more detailed survey of particular aspects of this area of chemistry. 相似文献
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Thomas E. Bitterwolf 《Journal of organometallic chemistry》2004,689(24):3939-3952
The discovery of the light initiated reaction of Fe(CO)5 to yield Fe2(CO)9 by Dewar and Jones in 1905 ushered in an era of the use of light to drive chemical reactions. This review seeks to examine selective chapters in this story by examining particularly significant reaction types in the context of their historical development. 相似文献
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Great advances have been made in the past decade in the field of NMR spectroscopy. Apart from the development of completely new areas of application, such as in solid-state chemistry, in materials science, in physiological chemistry, and in medicine, with the introduction of new pulse spectroscopic methods and the application of high magnetic field strengths important progress has also been made in the traditional field of high-resolution NMR spectroscopy. Thus, among other things, the observation of metal resonances has been facilitated and new areas of application have been opened up in inorganic and organometallic chemistry. In this review, recent detection methods for spin-1/2 and quadrupolar metal nuclei are presented and discussed. The use of metal-NMR spectroscopy with respect to problems of a typical chemical nature, mainly from the field of organometallics, is demonstrated for a number of selected metal nuclei (25Mg, 27Al, 49Ti, 57Fe, 59Co, 61Ni, 91Zr, 103Rh, and 195Pt). Relations found empirically between chemical shifts and coordination number, oxidation number, and electronic configuration of a metal bound in a complex are emphasized. Furthermore, cases in which the chemical shifts of metal nuclei can be interpreted in terms of the energy difference of frontier orbitals are presented. This aspect leads to the establishment of a relationship between chemical reactivity and NMR parameters for a series of related compounds. 相似文献
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W. M. H. Sachtler 《Angewandte Chemie (International ed. in English)》1968,7(9):668-681
Studies on the adsorption of gases such as xenon, hydrogen, nitrogen, and carbon monoxide on the surface of a single crystal of tungsten with the aid of field-emission and field-ion microscopy have, in the past few years, led to new, fundamental insights into chemisorption and heterogeneous catalysis. Important phenomena which were discoverd and elucidated by these techniques include the pronounced face specificity of the adsorption, the fact that several different adsorption complexes of a gas are found on one and the same crystal face, and the rearrangement of the surface atoms through chemisorption. Many of the interpretations thus gained for the systems studied can also be generalized for other chemisorption complexes. 相似文献
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This article covers 50 years of coordination chemistry of transition metal complexes and metal-sulfur aggregates involving thiolate-incorporating ligands by reviewing selected examples. The studies in the coordination chemistry of sulfur-rich ligands have been undoubtedly triggered and fed by the concomitant development of bioinorganic chemistry, particularly of iron-sulfur enzymes. The review is broken down in five sections, which examine complexes of increasing nuclearity, including binuclear complexes based on compartmental macrocyclic ligands. We show also how ligand engineering has allowed the researchers in the field to control the nuclearity of the complexes, which was a particularly difficult task for sulfur-based ligands, as thiolates show a strong tendency to coordinate to more than one metal cation at once. 相似文献
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The field of medicinal inorganic chemistry is rapidly advancing. In particular organometallic complexes have much potential as therapeutic and diagnostic agents. The carbon‐bound and other ligands allow the thermodynamic and kinetic reactivity of the metal ion to be controlled and also provide a scaffold for functionalization. The establishment of structure–activity relationships and elucidation of the speciation of complexes under conditions relevant to drug testing and formulation are crucial for the further development of promising medicinal applications of organometallic complexes. Specific examples involving the design of ruthenium and osmium arene complexes as anticancer agents are discussed. 相似文献
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Kendahl L. Walz Mitra Michael Riehs Andrei Draguicevic William A. Swann Christina W. Li Alexandra Velian 《Angewandte Chemie (International ed. in English)》2023,62(49):e202311575
Black phosphorus (bP) is a two-dimensional van der Waals material unique in its potential to serve as a support for single-site catalysts due to its similarity to molecular phosphines, ligands quintessential in homogeneous catalysis. However, there is a scarcity of synthetic methods to install single metal centers on the bP lattice. Here, we demonstrate the functionalization of bP nanosheets with molecular Re and Mo complexes. A suite of characterization techniques, including infrared, X-ray photoelectron and X-ray absorption spectroscopy as well as scanning transmission electron microscopy corroborate that the functionalized nanosheets contain a high density of discrete metal centers directly bound to the bP surface. Moreover, the supported metal centers are chemically accessible and can undergo ligand exchange transformations without detaching from the surface. The steric and electronic properties of bP as a ligand are estimated with respect to molecular phosphines. Sterically, bP resembles tri(tolyl)phosphine when monodentate to a metal center, and bis(diphenylphosphino)propane when bidentate, whereas electronically bP is a σ-donor as strong as a trialkyl phosphine. This work is foundational in elucidating the nature of black phosphorus as a ligand and underscores the viability of using bP as a basis for single-site catalysts. 相似文献
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Prof. Dr. Achim Müller Dr. Alice Merca Dr. Ahmed Jasim M. Al‐Karawi Somenath Garai Dr. Hartmut Bögge Dr. Guangfeng Hou Prof. Dr. Lixin Wu Dr. Erhard T. K. Haupt Prof. Dr. Dieter Rehder Fadi Haso Prof. Dr. Tianbo Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(51):16310-16318
Unique properties of the two giant wheel‐shaped molybdenum‐oxides of the type {Mo154}≡[{Mo2}{Mo8}{Mo1}]14 ( 1 ) and {Mo176}≡[{Mo2}{Mo8}{Mo1}]16 ( 2 ) that have the same building blocks either 14 or 16 times, respectively, are considered and show a “chemical adaptability” as a new phenomenon regarding the integration of a large number of appropriate cations and anions, for example, in form of the large “salt‐like” {M(SO4)}16 rings (M=K+, NH4+), while the two resulting {Mo146 (K(SO4))16} ( 3 ) and {Mo146 (NH4(SO4))16} ( 4 ) type hybrid compounds have the same shape as the parent ring structures. The chemical adaptability, which also allows the integration of anions and cations even at the same positions in the {Mo4O6}‐type units of 1 and 2 , is caused by easy changes in constitution by reorganisation and simultaneous release of (some) building blocks (one example: two opposite orientations of the same functional groups, that is, of H2O{Mo?O} ( I ) and O?{Mo(H2O)} ( II ) are possible). Whereas Cu2+ in [(H4CuII5)MoV28MoVI114O432(H2O)58]26? ( 5 a ) is simply coordinated to two parent O2? ions of {Mo4O6} and to two fragments of type II , the SO42? integration in 3 and 4 occurs through the substitution of two oxo ligands of {Mo4O6} as well as two H2O ligands of fragment I . Complexes 3 and now 4 were characterised by different physical methods, for example, solutions of 4 in DMSO with sophisticated NMR spectroscopy (EXSY, DOSY and HSQC). The NH4+ ions integrated in the cluster anion of 4 “communicate” with those in solution in the sense that the related H+ ion exchange is in equilibrium. The important message: the reported “chemical adaptability” has its formal counterpart in solutions of “molybdates”, which can form unique dynamic libraries containing constituents/building blocks that may form and break reversibly and can lead to the isolation of a variety of giant clusters with unusual properties. 相似文献
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Alexandra Inayat Ayman Makky Jose Giraldo Andreas Kuhnt Corinna Busse Prof. Dr. Wilhelm Schwieger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(26):8161-8169
An in situ method for the growth of ZnO nanocrystals on Zn/Al mixed metal oxide (MMO) surfaces is presented. The key to this method is the thermal treatment of Zn/Al layered double hydroxides (Zn/Al LDHs) in the presence of nitrate anions, which results in partial demixing of the LDH/MMO structure and the subsequent crystallization of ZnO crystals on the surface of the forming MMO layers. In a first experimental series, thermal treatment of Zn/Al LDHs with different fractions of nitrate and carbonate in the interlayer space was examined by thermogravimetry coupled with mass spectrometry (TG‐MS) and in situ XRD. In a second experimental series, Zn/Al LDHs with only carbonate in the interlayer space were thermally treated in the presence of different amounts of an external nitrate source (NH4NO3). All obtained Zn/Al MMO samples were analysed by electron microscopy, nitrogen physisorption and powder X‐ray diffraction. The gas phase formed during nitrate decomposition turned out to be responsible for the formation of crystalline ZnO nanoparticles. Accordingly, both interlayer nitrate and the presence of ammonium nitrate led to the formation of supported ZnO nanocrystals with mean diameters between 100 and 400 nm, and both methods offer the possibility to tailor the amount and size of the ZnO crystals by means of the amount of nitrate. 相似文献
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甲硫醇、甲醇在金属表面上的分解反应性能比较研究 总被引:2,自引:1,他引:1
用键级守恒-Morse势法比较了XH3SH、CH3OH在Ni(111)、Pt(111)和Cu(111)面上的热分解反应性能.结果表明,由Ni至Pt再至Cu,CH3SH中C-S键断裂几率降低,而S-H键裂相对几率增加,而在Cu上仅发生S-H键裂.CH3OH在Ni上易解离为CH3和CH3O-,在Pt、Cu上则较难解离.按Ni、Pt、Cu的顺序,CH3S-选择性断裂C-S键的几率增加,而CH3O-则选择性断裂C-H键的几率增加.CH3XH、CH3X-(X=O,S)解离活化能垒依Ni、Pt、Cu的顺序增加,CH3OH在Ni上最终解离为CO,而在Cu上则解离为H2CO. 相似文献
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A comparison of the concept of volume increments created by W. Biltz with that based on quantum mechanical calculations by R.F.W. Bader was performed for crystal structures of binary metal nitrides and ‐subnitrides. The mutual comparison of both concepts permits insights into the bonding relationships of these compounds and reveals the considerable range of volume demand of a strongly polarisable bonding partner, such as the nitride ion. Finally it becomes clear that the Biltz volume increments show a quantum‐chemical relevance in the chemistry of solids. 相似文献