Halide complexes organic, carbonylations

The presence of halides in the coordination sphere with aldehydes is important as zinc halides are typically used in organic synthesis as organic carbonyl activators. Large excesses of aldehydes and anhydrous zinc halides were necessary. Both monomeric and polymeric structures with halide bridges were observed. Tetrahedral geometries were observed for mixed ligand, aldehyde, and halide complexes.353... 

Thallium(i) salts have long been used in reactions with organic and organometallic halide complexes as a means of activating the halide by removal as insoluble T1X. However, the thallium ions proved not to be innocent bystanders, and numerous examples were reported in COMC (1995) where the metal-bound thallium complexes were formed. Deliberate reactions of thallium(i) and thallium(m) salts with metal carbonyl anions have yielded a variety of complexes of the form T1 MLJ3. In the past decade, new examples of metal carbonyl derivatives of thallium have been prepared (see Table 2). In addition, the propensity for Tl+ to form adducts with 16-electron noble metal complexes has been exploited. 

PTC and Metal Complexes Catalyzed Carbonylation of Organic Halides... 

Phase-Transfer- and Metal-Complexes-Catalyzed Carbonylation of Organic Halides. Carbonylation of organic halides catalyzed by transition metals is a general and efficient method of manufacturing of carboxylic acids. 

Other relevant material is contained in reviews on homogeneous catalysis of organic reactions by transition metal complexes, highly reduced metal carbonyl complexes, phosphine complexes of the early transition metal complexes and the lanthanoids, metal NMR spectra of transition metal organometallic systems, the coordination chemistry of C-Nitroso-compounds, mono-Cp halide complexes of the d- and/-block, and organometallic chemistry in the gas phase. o... 

Kobayashi, T. and Tanaka, M. (1986) Acylation of active methylene compounds via palladium complexcarbonylative cross-coupling of organic halides. Tetrahedron Letters, 27,4745-4748. 

When complex organic systems have evolved in nature, they are frequently made by the combination of carboxy carbonyl groups and the heteroatoms of alcohols, amines, or thiols. Why The addition-elimination processes introduced in Chapter 19 provide mechanistic pathways of relatively low activation energy for the interconversion of variously substituted carboxylic acid derivatives, many of which play central roles in biology (Chapter 26). Chemists find these compounds similarly useful, as we shall see in this chapter, which deals with the chemistry of four major carboxylic acid derivatives halides, anhydrides, esters, and amides. Each has a substituent, L, that can function as a leaving group in substitution reactions. We already know, for instance, that displace-O... 

The electroreductive carbonylation and carboxylation of organic halides catalyzed by different metal complexes is summarized in Section 9.10.5. Electrogenerated Ni° complexes containing bpy193-196 or pentamethyldiethylenetriamine196-199 ligands are effective catalysts for the electrosynthesis of... 

The complex [Ni(bpy)2]2+ catalyzes the electroreductive coupling of organic halides and carbon monoxide into ketones under a CO atmosphere,226 or in the presence of a metal carbonyl,227 especially iron pentacarbonyl. Unsymmetrical ketones have been obtained from mixtures of two different organic halides.228 CO is very reactive towards reduced Ni° species to form the stable [Ni°(bpy)(CO)2]° complex, which probably evolves to a transient arylnickel [Nin(bpy)(R)(CO)X]° complex in the presence of both ArX and [Ni°(bpy)]° species.229,230... 

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