Aryl derivatives carbon-transition metal bonds

The stabilities of the metal-carbon bond formed from oxidative additions are as varied as their mechanistic pathways. Metal-carbon bond strengths increase going down a triad in an isostructural series of complexes. Alkyl migration to CO ligands on the metal to form acyl derivatives is more facile in first-row transition metals because of their lower metal-carbon bond energies. The thermal stability of alkyls vs. acyls does not follow any pattern, except that the availability of a sixth coordination site in ML (acyl) complexes favors the alkyl carbonyl isomer. The corresponding acyl, which can be made by running the reaction of the alkyl or aryl halide in CO (at 1-3 atm), is more stable by... 

Negishi, E., King, A. O., Okukado, N. Selective carbon-carbon bond formation via transition metal catalysis. 3. A highly selective synthesis of unsymmetrical biaryls and diarylmethanes by the nickel- or palladium-catalyzed reaction of aryl- and benzylzinc derivatives with aryl halides. J. Org. Chem. 1977,42, 1821-1823. 

Some interesting developments concerning C-C bond formation using organoborane coupling reactions have been made. 9-Alkyl-9-BBN derivatives (144) react with aryl and benzyl halides in the presence of transition metal catalysts and carbon monoxide to give... 

The salts of unsaturated mono- and dicarboxylic acids have received the most attention among the MCMs of ionic type. The ionic bond in a pure state is only present in salts of alkaline and alkaline earth metals. In other compounds, especially in the case of transition metal compounds, it is complicated by an admixture of covalent bonding. The general method for their synthesis, for examples 33, comes by the interaction of salts, (hydr)oxides and (hydro)carbonates of the metals or their mixtures as well as alkyl(aryl)-derivatives with unsaturated mono- and dicarboxylic acids or their anhydrides (Eq. (4-5) (see Experiment 4-1, Section 4,6). 

The reaction of CO2 with a metal hydride produces formate complexes M-0C(0)H, not formyl derivatives M-C(0)0H, and the insertion into M-C bonds gives the appropriate carboxylate compounds M-0C(0)R. In a similar fashion, the reactions with M-OH and M-OR (R = alkyl, aryl) generate the corresponding bicarbonate M-0C(0)0H and carbonate M-0C(0)0R species, respectively. The reaction of CO2 with a zinc hydroxide moiety is particularly important in biological systems, namely, for the reversible hydration of CO2 to HCOs catalyzed by Zn(ll) in carbonic anyhdrases. Moreover, it has been postulated that the insertion of CO2 into M-O bonds is essential in the co-polymerization of CO2 and epoxides and in the preparation of cyclic carbonates and polycarbo-In a similar vein, the insertion of CO2 into the M-N bond of both main group and transition metal... 

Aliphatic and aromatic amines are also widely available from nature or industry. However, studies on their chemical transformation through transition metal-catalysed carbon-nitrogen bond cleavage are relatively scarce. Recently, several nickel-catalysed transformation of amine derivatives including aryl or benzylammonium salts, N-atyl amides and carbamates, as well as JV-sulfonyl aziridines were reported. 

Transition metal compounds containing o--bonded alkyl or aryl groups were rare until the 1960 s. It has been found that the presence of ligands such as CO, C5H5, or PR3 on transition metals greatly enhances the ability of transition metals to form o--bonded organometallic compounds. Transition metal-carbon a bonds are often produced by metathesis reactions in which one product is the organometallic compound and the other is a simple salt, reactions (11), (12). Transition metal fluorocarbon derivatives have also been... 

In this article the term organometallic compound includes alkyl and aryl derivatives of the rare earths—the transition metals of group III, scandium, yttrium, lanthanum and the lanthanides cerium to liitetium with covalent metal-to-carbon a-bonds, as well as the so-called 77-complexes with more than monohapto metal-to-carbon bonds, for example cyclopentadienyl and olefin complexes, metal acetylides, but not carbonyls, cyanides and isocyanide complexes. Derivatives of scandium, yttrium and lanthanum are included and discussed together with the compounds of the lanthanides, because of many similarities in the synthesis and the chemistry of these organometallic derivatives of the rare earths. 

By varying the metal complex anion and RX, a wide variety of metal compounds containing transition metal-carbon cr-bonds have been prepared directly by this reaction. In addition, acyl metal derivatives prepared by this method may be decarbonylated to give alkyl and aryl metal complexes. 

The organometallic compounds prepared from alkali metal derivatives of metal carbonyls include compounds in which a transition metal of a metal carbonyl residue is cr-bonded to another atom such as a carbon atom in an alkyl, acyl, aryl, or perfluoroalkyl group, to the heavier congeners of carbon —silicon, germanium, tin, and lead—to mercury and gold which form unusually stable compounds, and even to other transition metals. The preparation and properties of all of these classes of compounds will be considered and, for the sake of completeness, a few related compounds prepared by routes other than those involving anionic metal carbonyl derivatives will be discussed. 

The possibilities for the formation of carbon-carbon bonds involving arenes have been dramatically increased in recent years by the use of transition metal catalysis. Copper-mediated reactions to couple aryl halides in Ulknann-type reactions [12, 13] have been known for many years, and copper still remains an important catalyst [14, 15]. However, the use of metals such as palladium [16,17] to effect substitution has led to such an explosion of research that in 2011 transition metal-catalyzed processes comprised more than half of the reactions classified as aromatic substitutions in Organic Reaction Mechanisms [18]. The reactions often involve a sequence outlined in Scheme 6.6 where Ln represents ligand(s) for the palladium. Oxidative addition of the aryl halide to the paiiadium catalyst is followed by transmetalation with an aryl or alkyl derivative and by reductive elimination to give the coupled product and legeuCTate the catalyst. Part 6 of this book elaborates these and related processes. 

Photochemical cleavage of metal-carbon bonds constitutes a brief part of a recent review on the photochemistry of metal carbonyls. Reviews of metal-alkyl and -aryl complexes have also appeared, one of which is concerned solely with metals in Groups IV— VII. The other deals with the formation, stability, and decomposition pathways of transition metal-carbon a-bonds, subjects of much interest in recent years. Consequently the recent isolation of the first stable methylene complex [Ta(Me)(CHa)(jj-C6H6)2] and its unequivocal characterization by a single-crystal JlT-ray diffraction study is of great interest in view of the probability that related derivatives are involved in the recently reported (see Vol, 4, p. 293) examples of a-hydride elimination in metal alkyls. 

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