Science of Synthesis

Malacria, M.; Aubert, C.; Renaud, J.-L., Science of Synthesis, (2001) 1, 486.

The most versatile route to organocobalt(III) complexes involves the reaction of nucleophilic cobalt(I) species with organic compounds. A wide range of cobalt(I) species, including vitamin B12s (a reduced form of cyanocobalamin and of the coenzyme) and the [Co(dmg)2py]− anion are known. They are very powerful nucleophiles and undergo rapid oxidative addition reactions with a variety of electrophiles.[‌204‌] They efficiently displace halide, tosylate, carboxylate, sulfate, and phosphate from the corresponding alkyl derivatives, and open epoxide and ethylimine rings. The cobalt(I) species are prepared by the in situ reduction of the appropriate cobalt(III) or cobalt(II) starting material using reducing agents such as sodium borohydride or sodium amalgam, followed by the addition of any one of a number of alkylating agents (‌Scheme 55‌). The [Co(dmg)2py]− anion can be formed by sodium borohydride reduction of ‌74‌ or in situ from cobalt(II) chloride, dimethylglyoxime, sodium hydroxide, pyridine, and sodium borohydride (‌Scheme 55‌).[‌205‌,‌206‌]

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References