Organometallic chemistry transmetalators

Transmetallation is probably the most frequently employed preparative procedure in organometallic chemistry, and perhaps the commonest variant on this route to new metal-carbon bonds is the interaction of a transition-metal halide MX and a hydrocarbyl derivative of a (usually) more electropositive metal M R ... 

The high reactivity of alkyllithium in the transmetalation often causes multiple alkylation of halogeno complexes of transition metals to produce anionic polyalkyl complexes (ate complexes). The reaction is classified into transmetalation in Scheme 5.1(iii). The most common and important ate complexes in organic and organometallic chemistry are organocuprates [22-24] (Eq 5.8). 

L.S., Eds., Transition Metal Alkyl Complexes Main-group Transmetallation and Insertion Chemistry in Comprehensive Organometallic Chemistry II, Vol. 12, Pergamon, Oxford, 1995, p. 131. 

In addition, a catalytic version of Tt-allylpalladium chemistry has been devel-oped[6,7]. Formation of the Tr-allylpalladium complexes by the oxidative addition of various allylic compounds to Pd(0) and subsequent reaction of the complex with soft carbon nucleophiles are the basis of catalytic allylation. After the reaction, Pd(0) is reformed, and undergoes oxidative addition to the allylic compounds again, making the reaction catalytic.-In addition to the soft carbon nucleophiles, hard carbon nucleophiles of organometallic compounds of main group metals are allylated with 7r-allylpalladium complexes. The reaction proceeds via transmetallation. These catalytic reactions are treated in this chapter. 

Yasuda S, Yorimitsu H, Oshima K (2008) Synthesis of aryliron complexes by palladium-catalyzed transmetalation between [CpFe(CO)2l] and aryl Grignard reagents and their chemistry directed toward organic synthesis. Organometallics 27 4025 027 Jonas K, Schieferstein L (1979) Simple route to Li- or Zn-metalated r -cyclopentadien-yliron-olefin complexes. Angew Chem Int Ed Engl 18 549-550... 

Chan, M.C.-W. and Che, C.-M. (1998) Application of 2,6-diphenylpyridine as a tridentate [C N C] dianionic ligand in organogold(III) chemistry. Structural and spectroscopic properties of mono- and binuclear transmetalated gold(III) complexes. Organometallics, 17, 3505-3511. 

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