Metalation theoretical aspects

Tousek J 1985 Theoretical Aspects of the Localized Corrosion of Metals (Rockport, MA TransTech) Boehni H 1987 Corrosion Mechanisms ed F Mansfeld (New York Dekker)... 

All ctfecis caused by electrostatic or electromagnetic inductions are termed Inductive Interferences. With the use t)f glass optical fibre cables in new installaiioiis. this effect is overcome automatically. Optical fibre cables, as discussed later, have no metal content and cany no electrical signals. Therefore the above discussion is more appropriate for existing installations and also to provide a theoretical aspect and moi c clarity on the phenomena of inductive interferences. These can also be applied to other fields rather than communications alone. 

The cycloaddition reactions of carbonyl compounds with conjugated dienes cannot be discussed in this context without trying to understand the reaction mechanistically. This chapter will give the basic background to the reactions whereas Chapter 8 dealing with theoretical aspects of metal-catalyzed cycloaddition reactions will give a more detailed description of this class of reactions, and others discussed in this book. 

Theoretical aspects of transition metal chemistry. L. G. Vanquickenbome, Comments Inorg. Chem., 1982, 2, 23-38 (37). 

The last two decades have seen a growing interest in the mechanism of inorganic reactions in solution. Nowhere is this activity more evident than in the topic covered by this review the oxidation-reduction processes of metal complexes. This subject has been reviewed a number of times previously, notably by Taube (1959), Halpern (1961), Sutin (1966), and Sykes (1967). Other articles and books concerned, wholly or partly, with the topic include those by Stranks, Fraser , Strehlow, Reynolds and Lumry , Basolo and Pearson, and Candlin et al ° Important recent articles on the theoretical aspects are those by Marcus and Ruff. Elementary accounts of redox reactions are included in the books by Edwards , Sykes and Benson . The object of the present review is to provide a more detailed survey of the experimental work than has hitherto been available. 

Theory has participated in all aspects of this area s development. The almost hand-waving arguments used to rationalize their chemical behavior need testing and will likely be replaced by more elegant quantitative discussions. The theoretical aspects( 77 ) and most physical property measurements(78) of small metal clusters have been recently reviewed. 

Torrent, M., Sola, M., and Frenking, G. (2000). Chem. Rev. 100, 439. A 54-page high-level paper dealing with theoretical aspects of processes in which metal complexes function as catalysts. 

Ruzic [278 ] considered the theoretical aspects of the direct titration of copper in seawaters and the information this technique provides regarding copper speciation. The method is based on a graph of the ratio between the free and bound metal concentration versus the free metal concentration. The application of this method, which is based on a 1 1 complex formation model, is discussed with respect to trace metal speciation in natural waters. Procedures for interpretation of experimental results are proposed for those cases in which two types of complexes with different conditional stability constants are formed, or om which the metal is adsorbed on colloidal particles. The advantages of the method in comparison with earlier methods are presented theoretically and illustrated with some experiments on copper (II) in seawater. The limitations of the method are also discussed. 

In this chapter, we will summarize the relevant theoretical studies on the reaction mechanisms of transition metal catalyzed borations. It is our hope that an overall picture can be given in a manner which can be easily understood without detailing all the theoretical aspects. It should be noted here that other comprehensive reviews, both experimental and theoretical, on the topic of catalytic boration reactions can also be found elsewhere in the literature [3-6]. 

Electronic and vibrational spectroscopy continues to be important in the characterization of iron complexes of all descriptions. Charge-transfer spectra, particularly of solvatochromic ternary diimine-cyanide complexes, can be useful indicators of solvation, while IR and Raman spectra of certain mixed valence complexes have contributed to the investigation of intramolecular electron transfer. Assignments of metal-ligand vibrations in the far IR for the complexes [Fe(8)3] " " were established by means of Fe/ Fe isotopic substitution. " A review of pressure effects on electronic spectra of coordination complexes includes much information about apparatus and methods and about theoretical aspects, though rather little about specific iron complexes. ... 

Theoretical Aspects of Metal Vinylidene and Allenylidene Complexes... 

Species (A) and (B) constitute the main class of unsaturated carbenes and play important roles as reactive intermediates due to the very electron-deficient carbon Cl [1]. Once they are coordinated with an electron-rich transition metal, metal vinylidene (C) and allenylidene (D) complexes are formed (Scheme 4.1). Since the first example of mononuclear vinylidene complexes was reported by King and Saran in 1972 [2] and isolated and structurally characterized by Ibers and Kirchner in 1974 [3], transition metal vinylidene and allenylidene complexes have attracted considerable interest because of their role in carbon-heteroatom and carbon-carbon bond-forming reactions as well as alkene and enyne metathesis [4]. Over the last three decades, many reviews [4—18] have been contributed on various aspects of the chemistry of metal vinylidene and allenylidene complexes. A number of theoretical studies have also been carried out [19-43]. However, a review of the theoretical aspects of the metal vinylidene and allenylidene complexes is very limited [44]. This chapter will cover theoretical aspects of metal vinylidene and allenylidene complexes. The following aspects vdll be reviewed ... 

The content of this book gathers in the same volume all aspects of vinylidene- and allenylidene-metal complexes, including the preparation of these organometallic carbon-rich systems with a metal-carbon double bond, their stoichiometric reactivity and theoretical aspects, and their applications in catalysis for the production of fine chemicals, mainly in the field of selective transformations of functional terminal alkynes. It provides essential general information on catalytic transformations of alkynes and their use in synthesis. 

The present volume comprises 17 chapters, written by 27 authors from 11 countries, and deals with theoretical aspects and structural chemistry of peroxy compounds, with their thermochemistry, O NMR spectra and analysis, extensively with synthesis of cyclic peroxides and with the uses of peroxides in synthesis, and with peroxides in biological systems. Heterocyclic peroxides, containing silicon, germanium, sulfur and phosphorus, as well as transition metal peroxides are treated in several chapters. Special chapters deal with allylic peroxides, advances in the chemistry of dioxiranes and dioxetanes, and chemiluminescence of peroxide and with polar effects of their decomposition. A chapter on anti-malarial and anti-tumor peroxides, a hot topic in recent research of peroxides, closes the book. 

---