Metal complexes applications

Stable Carbene-Transition Metal Complexes Applications in Catalysis.. . 358... 

The protonated form of poly(vinyl amine) (PVAm—HC1) has two advantages over many cationic polymers high cationic charge densities are possible and the pendent primary amines have high reactivity. It has been applied in water treatment, paper making, and textiles (qv). The protonated forms modified with low molecular weight aldehydes are useful as fines and filler retention agents and are in use with recycled fibers. As with all new products, unexpected applications, such as in clear antiperspirants, have been found. It is useful in many metal complexation applications (49). 

The NMR has provided an invaluable tool in the elucidation of both the static and dynamic stereochemistry of metal complexes. Applications to both diamagnetic and paramagnetic species have been rewarding. In particular, the unique role of NMR as a mechanistic probe for the elucidation of fluxional processes in polynuclear metal carbonyl complexes should be noted. 

Electrochemistry of Metal Complex Applications from Electroplating to Oxide Layer Formation, First Edition. Arvydas Survila. 

Ford, PC. Lever, A. B. P. (eds.). Photochemistry and Photophysics of Metal Complexes Applications to Solar Energy. (Special issue containing a collection of papers presented at the Symposium of the 1984 International Chemical Congress of the Pacific Basin Societies, Honolulu, 17-19 December 1984), Coord. Chem. Revs. 1985,64. 

Prier CK, Rankic DA, MacMillan DWC (2013) Visible light photoredox catalysis with transition metal complexes applications in organic synthesis. Chem Rev 113 5322-5363... 

Magnetic circular dicliroism (MCD) is independent of, and thus complementary to, the natural CD associated with chirality of nuclear stmcture or solvation. Closely related to the Zeeman effect, MCD is most often associated with orbital and spin degeneracies in cliromophores. Chemical applications are thus typically found in systems where a chromophore of high symmetry is present metal complexes, poriihyrins and other aromatics, and haem proteins are... 

V S, C M Kelly and C R Landis 1991. SHAPES Empirical Force-Field - New Treatment of igular Potentials and Its Application to Square-Planar Transition-Metal Complexes. Journal of American Chemical Society 113 1-12. 

Rappe A K, K S Colwell and C J Casewit 1993. Application of a Universal Force Field to Metal Complexes. Inorganic Chemistry 32 3438-3450. 

The direct connection of rings A and D at C l cannot be achieved by enamine or sul> fide couplings. This reaction has been carried out in almost quantitative yield by electrocyclic reactions of A/D Secocorrinoid metal complexes and constitutes a magnificent application of the Woodward-Hoffmann rules. First an antarafacial hydrogen shift from C-19 to C-1 is induced by light (sigmatropic 18-electron rearrangement), and second, a conrotatory thermally allowed cyclization of the mesoionic 16 rc-electron intermediate occurs. Only the A -trans-isomer is formed (A. Eschenmoser, 1974 A. Pfaltz, 1977). 

Indicator Chemical name Dissociation constants and colors of free indicator species Colors of metal-indicator complexes Applications... 

Olefin Hydroformylation (The Oxo Process). One of the most important iadustrial applications of transition-metal complex catalysis is the hydroformylation of olefins (23), ihusttated for propjdene ... 

G. W. ParshaH, Homogeneous Catalysis The applications and Chemistry of Catalysis by Soluble Transition Metal Complexes,Johm. Wiley Sons, Inc., New York, 1980, 240 pp. An excellent treatment of catalysis by coordination compounds. 

Bismuth heterocycles, 1, 539-561 Bismuthiol I metal complexes, 6, 565 IR spectra, 6, 552 ring structure, 6, 561 structure, 6, 557 Bismuthiol II metal complexes, 6, 565 IR spectra, 6, 552 Bisnorisopenicillin, 7, 332, 333 Bisnorpenicillin V, 7, 331 Bis( l,3,4-oxathiazol-2-ones) applications, 6, 945 Bisoxiranes synthesis, 7, 42 Bi(spiroisoxazolines) synthesis, 6, 108 Bi(spirophosphoranes) polytopal rearrangements, 1, 529 reactions, 1, 535 Bispyranones synthesis, 3, 793 a,oj-Bispyranones, alkylene-irradiation, 3, 678... 

Cryptands, 7, 731-761 alkali metal complexes NMR, 7, 740 reactivity, 7, 743-744 alkaline earth complexes reactivity, 7, 743-744 anion complexes, 7, 747-748 applications, 7, 753-761 as biological models, 7, 753-754 bis-tren... 

J Li, L Noodleman, DA Case. Electronic structure calculations Density functional methods with applications to transition metal complexes. In EIS Lever, ABP Lever, eds. Inorganic Electronic Structure and Spectroscopy, Vol. 1. Methodology. New York Wiley, 1999, pp 661-724. 

Elemental Huonne as a Legitimate Reagent for Selective Fluonnation of Orgamc Compounds Fluoroaromatic Compounds Synthesis, Reactions, and Commercial Applications New Aspects of Carbonylations Catalyzed by Transition Metal Complexes Polyfluoroaromatics An Excursion m Carbamon Chemistry ... 

A related example is the reaction of NbCls and thf with (Me3Si)2NN(SiMe3)2 in CH2CI2 to give an 80% yield of [(/Lt-N2) NbCl3(th02 2]- Occasionally an N=N triple bond can be formed within a metal complex, e.g. by reaction of coordinated NH3 with HNO2, but this method is of limited application, e.g. ... 

Since no special ligand design is usually required to dissolve transition metal complexes in ionic liquids, the application of ionic ligands can be an extremely useful tool with which to immobilize the catalyst in the ionic medium. In applications in which the ionic catalyst layer is intensively extracted with a non-miscible solvent (i.e., under the conditions of biphasic catalysis or during product recovery by extraction) it is important to ensure that the amount of catalyst washed from the ionic liquid is extremely low. Full immobilization of the (often quite expensive) transition metal catalyst, combined with the possibility of recycling it, is usually a crucial criterion for the large-scale use of homogeneous catalysis (for more details see Section 5.3.5). 

In comparison with traditional biphasic catalysis using water, fluorous phases, or polar organic solvents, transition metal catalysis in ionic liquids represents a new and advanced way to combine the specific advantages of homogeneous and heterogeneous catalysis. In many applications, the use of a defined transition metal complex immobilized on a ionic liquid support has already shown its unique potential. Many more successful examples - mainly in fine chemical synthesis - can be expected in the future as our loiowledge of ionic liquids and their interactions with transition metal complexes increases. 

In a catalytic asymmetric reaction, a small amount of an enantio-merically pure catalyst, either an enzyme or a synthetic, soluble transition metal complex, is used to produce large quantities of an optically active compound from a precursor that may be chiral or achiral. In recent years, synthetic chemists have developed numerous catalytic asymmetric reaction processes that transform prochiral substrates into chiral products with impressive margins of enantio-selectivity, feats that were once the exclusive domain of enzymes.56 These developments have had an enormous impact on academic and industrial organic synthesis. In the pharmaceutical industry, where there is a great emphasis on the production of enantiomeri-cally pure compounds, effective catalytic asymmetric reactions are particularly valuable because one molecule of an enantiomerically pure catalyst can, in principle, direct the stereoselective formation of millions of chiral product molecules. Such reactions are thus highly productive and economical, and, when applicable, they make the wasteful practice of racemate resolution obsolete. 

Investigations of silicon-metal systems are of fundamental interest, since stable coordination compounds with low valent silicon are still rare [64], and furthermore, silicon transition-metal complexes have a high potential for technical applications. For instance, coordination compounds of Ti, Zr, and Hf are effective catalysts for the polymerization of silanes to oligomeric chain-silanes. The mechanism of this polymerization reaction has not yet been fully elucidated, but silylene complexes as intermediates have been the subject of discussion. Polysilanes find wide use in important applications, e.g., as preceramics [65-67] or as photoresists [68-83],... 

The growing interest in volatile silyl-metal complexes for chemical vapor deposition reactions should also be mentioned. This technique is extremely useful for the preparation of silicide films in microelectronic devices. Further examples of applications of silicon-metal compounds are given in the appropriate sections. 

Two commonly used synthetic methodologies for the synthesis of transition metal complexes with substituted cyclopentadienyl ligands are important. One is based on the functionalization at the ring periphery of Cp or Cp metal complexes and the other consists of the classical reaction of a suitable substituted cyclopentadienyl anion equivalent and a transition metal halide or carbonyl complex. However, a third strategy of creating a specifically substituted cyclopentadienyl ligand from smaller carbon units such as alkylidynes and alkynes within the coordination sphere is emerging and will probably find wider application [22]. 

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