Zinc-transition metal bonds, organozinc

A number of compounds having a direct zinc transition metal bond are known for long time, that is, zinc-bis(transition metal) such as Zn[Co(C04)]2 and transition metal zinc halides such as (CO)4Fe(ZnCl)2. However, organozinc-transition metal compounds RZn-TM are comparatively more recent. They can be prepared by hydrocarbon elimination between a diorganozinc derivative and a transition metal hydride (see Hydrides) (equation 35), but dialkyl- and diarylzinc compounds usually fail to react or react very slowly. Furthermore, when they do react they give unstable products that show a very strong tendency to disproportionate and cannot be isolated (equation 36). 

The report by Resa et al. on a hydrocarbon-soluble, molecular compound of monovalent zinc, namely decamethyl-dizincocene, therefore caused considerable excitement among inorganic and organometallic chemists alike.233 Organozinc compounds with direct zinc-transition metal bonds have also been reported recently, and this area of organozinc chemistry with direct metal-metal bonds will undoubtedly witness considerable growth in the near future. 

The synthesis of functionalized zinc organometallics can be accomplished with a variety of methods that have been developed in recent years. The intrinsic moderate reactivity of organozinc reagents can be dramatically increased by the use of the appropriate transition metal catalyst or Lewis acid. Furthermore, the low ionic character of the carbon-zinc bond allows the preparation of a variety of chiral zinc organometallics with synthetically useful configurational stability. These properties make organozinc compounds ideal inteimediates for the synthesis of complex and polyfunctionalized organic molecules. 

A further asset of this class of reagents is the covalent character of the zinc-carbon bond, this allows these organozinc reagents to undergo trans-metallation reactions smoothly and cleanly with a wide variety of transition metal salts. Thus, the zincated phosphine 5 can be reacted with (acetonitrile)... 

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