Organometallic compounds, of transition

III. Catalysts Based on the Use of Organometallic Compounds of Transition Metals. 184... 

In essence the active centers for catalytic polymerization of olefins are organometallic complexes of transition metals. For this reason a search for individual organometallic compounds that would possess catalytic activity in olefin polymerization is of great interest. The first attempts to use organometallic compounds of transition metals as catalysts for olefin polymerization were made long ago [e.g. CH3TiCl3 as a catalyst for polymerization of ethylene 116). However, only in recent years as a result of the application of relatively stable organometallic compounds of transition... 

B. Catalysts Formed by Interaction of Organometallic Compounds of Transition Metals with Oxide Supports... 

Recently some information became available on a new type of highly active one-component ethylene polymerization catalyst. This catalyst is prepared by supporting organometallic compounds of transition metals containing different types of organic ligands [e.g. benzyl compounds of titanium and zirconium 9a, 132), 7r-allyl compounds of various transition metals 8, 9a, 133), 7r-arene 134, 185) and 71-cyclopentadienyl 9, 136) complexes of chromium]. 

The catalysts formed by the support of organometallic compounds of transition elements are also of great interest for nonpolymerization reactions. Generally speaking, these catalysts can be used in three various states (a) in the initial state, (b) after reduction, and (c) after oxidation... 

This monograph contains enthalpies of formation, heat capacities, entropies, and metal-ligand bond dissociation enthalpies of organometallic compounds of transition and main group elements. 

YU. I. Yermakov, Supported catalysts obtained by interaction of organometallic compounds of transition elements with oxide supports, Catal. Rev. Sci. Eng. 13(1), 77-120 (1976). 

It was later found that stable organometallic compounds of transition metals exhibiting very low polymerization activity could be transformed into high-activity catalysts when deposited on silica, alumina, or silica-alumina.287-289 Interaction of surface hydroxyl groups with the organometallic compounds such as chromocenes, benzyl, and Tt-allyl complexes results in the formation of surface-bound organometallic complexes (41-43) 289-291... 

In this chapter we will restrict our discussion of organometallic compounds to the alkyl and aryl compounds of magnesium and lithium, and the sodium and potassium salts of 1-alkynes. These substances normally are derived directly or indirectly from organohalogen compounds and are used very widely in organic synthesis. Organometallic compounds of transition metals and of boron are discussed in Chapters 11 and 31. 

Organometallic compounds of transition metals with alkyl-to-metal bonds for many years were regarded as highly unstable substances and prone to dissociate into radicals that would couple or disproportionate, as illustrated by the following sequence ... 

Dative covalent bonds, or coordinate covalent bonds, are those in which electrons are shared (as in all covalent bonds), but in which both electrons involved in each bond are contributed from the same atom. Such bonds occur in organometallic compounds of transition metals having vacant d orbitals. It is beyond the scope of this book to discuss such bonding in detail the reader needing additional information should refer to works on organometallic compounds.12 The most common organometallic compounds that have dative covalent bonds are carbonyl compounds, which are formed from a transition metal and carbon monoxide, where the metal is usually in the -1, 0, or +1 oxidation state. In these compounds the carbon atom on the carbon monoxide acts as an electron-pair donor ... 

The most important complexes involving carbon-containing ligands in which carbon is bound to the metal are discussed separately those of carbon monoxide in Chapter 16, organometallic compounds of transition elements, and organometallic compounds of the main group elements in the corresponding chapters. 

Al. F. A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry, 2nd ed. Wiley, New York, 1966. Probably the best general introduction to organo-transition metal chemistry. See Chapter 27 (pp. 719-760) Complexes of w-acceptor (w-acid) ligands Chapter 28 (pp. 761-795) Organometallic compounds of transition metals. 

There are also catalysts known in which ACs are formed during the direct interaction between the transition metal compound and the monomer without participation of special cocatalysts (so-called one-component catalysts). Examples of one-component catalysts are chromium oxide catalysts, lower halides of transition metals (titanium dichloride) and catalysts prepared by precipitating organometallic compounds of transition elements on oxide carriers... 

Telomerization is defined as an oligomerization of dienes accompanied by addition of a heteroatom or carbon nucleophilic reagent10. It is catalyzed by various organometallic compounds of transition metals, especially palladium compounds. The nucleophiles, such as water, alcohols, amines or carboxylic acids, as well as enamines, nitroalkanes and stabilized carban-ions, are mainly introduced in the terminal position of the dimeric molecule in excellent yield10. It is also possible to direct the reaction towards an internal product functionalization. Telo-merizations with heteronucleophiles are regarded as heterocarborative addition reactions and are described in Section 1.5.8.4. 

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