0 Hits

  • Previous / Next

You are using Science Of Synthesis as a Guest.
Please login to access the full content or check if you have access via From Cobalt(I) Complexes

DOI: 10.1055/sos-SD-001-00322

Malacria, M.; Aubert, C.; Renaud, J.-L.Science of Synthesis, (20011486.

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]

Meeeee 88 Meeeeeeee ee Meeeee(MMM) Meeeeeeee eeee Meeeee(M) Meeeeee[‌888‌‌888‌]

Meeeee(M) eeeeeee eee eeee eeeeeee ee eeeeeeeeee eeeeeeeeeeee eeeeeeee ee e eeeeeee ee eeeeeee, eeeeeeeeee eeeeeee 88[‌888‌,‌888‌] eee eeeeee,[‌888‌] ee eeee 8,8-eeeeeeeeeeeeeeee eeeeeeeee eeee ee 88.

Me eee eeeee eeee, ee eeee eeeee eeeee eee eeeeee(M) eeeeeeeee eee eeeeeeee e eeeeee ee eeee eeeeeeee eeeeeeee eeeee eee eeeee eeee eeeeeeeeee eeeeee ee e eeeeeeeee eeeeee ee eee eeeeeeeeeeee eeeeee(M) eeeeeee.

Meeeeeeeeeee Meeeeeeee

Meeeeeeeeeeeeeee(MMM) eeee Meeeee(M) Meeeeee; Meeeeee Meeeeeeee:[‌888‌,‌888‌]

Mee eeeeeeeee eeee eeeeeeeee eeeee M8. Mee eeeeeeee eeee eeeeeeeeeeee ee eeeeeeeeee eeee M8 ee eeeeeeee eee ee. 8eee·eM8. Meeeeeeee eee eee eeeeeeeee ee eeeee-eeeeeeeee eeeeeeeeeeeeeeee eeee eeeeeeeee ee e eeee eeee eeee eee eeeeee eeeeee eee eee eee eeeeee eeeeeee ee eeeeeeee eeee. Meeeee eeeeeeeeeeeeee eee eeeeeeeee eeeeeeeeeeeee, eeeee eeeeeeeeeeee eeeeeeee, eeee-eeeeeee eeeeeee, eee eeeeeeee ee eeeeee eeeeeeeee eeee M8 ee eeee eeee eeeeeeeee.

Meeeeeeeeeeeeeeeee(eeeeeeee)eeeeee(MMM) Meeee (88) Meeee Meeeee(MM) Meeeeeee:

MeMe88M8M (8.888e, 88.8eeee) eee M8eee (8.888e, 88.8eeee) eeee eeeeeeee ee e 888-eM eeeee-eeeeeeee eeeee eeeeeeeeee MeMM (888eM). Mee eeee eee eeeeeee ee 8°M, eeeeeeee ee eeeeeeee ee eeeeeeee (8.8eM, 88.8eeee) eee eeee 88% ee MeMM (8.88e, 88.8eeee). Meeee 88eee, MeMM8 (8.888e, 88.8eeee) eee eeeee ee eeeeeeee, eeeeeeeee eee eeee eeeee-eeeee eeeee 88.

Meeeeeeeeeeeeeeeee(eeeeeeee)eeeeee(MMM) Meeee (88) Meeee Meeeee(eeeeeeeeeeeeeeeeee)(eeeeeeee)eeeeee(MMM) (88):

M eeee ee 88 (8.888e, 88.8eeee) ee eeeeeee eeeeeeeee MeMM (88eM) eee eeeeeeeeeeee ee eeeeeeee eeee M8 eee 88eee eeeee eeeeeee ee 8°M. MeMM8 (8.888e, 88.8eeee) eee eeeee eeeeeeeeeee eee eee eeee eeeeee eeee eeeee-eeeee, eeeeeeeeee eee eeeeeeeee ee 88.

Meeeeeeeeeeeeeee(MMM) 88:

Me e eeeeee (8°M) eeee ee 88 ee MeMM ee MeMM eee eeeee e eeee ee eee eeeee eeeeeee ee eee ee eee eeeeeeeeeeeee eeeeeeee. Meeee eeeee eeeeeee ee 8°M, eee eeeeeee eee eeeeee ee ee. Mee eeee eee eeeeeeeee ee MMM eeeee eee eeeeeeeeeeeee ee eee eeeee eeeeeee. Meeee eeeeeeeeee, eee eeeee eeeeeee eee eeeeeeeee ee eeeeee eeeeeeeeee eee eeeeee eeee e eeeeee eeeeee eeee eeeeee eee eee eeeeeeeeeeee MeMMe. Meeeeeeeeeeeee eeeeeeee eee eeeeeeeeeeeeeeee 88.