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Cobalt: Organometallic Chemistry

  1. Keith T. Quisenberry,
  2. Timothy P. Hanusa

Published Online: 15 DEC 2011

DOI: 10.1002/9781119951438.eibc0045

Encyclopedia of Inorganic and Bioinorganic Chemistry

Encyclopedia of Inorganic and Bioinorganic Chemistry

How to Cite

Quisenberry, K. T. and Hanusa, T. P. 2011. Cobalt: Organometallic Chemistry . Encyclopedia of Inorganic and Bioinorganic Chemistry. .

Author Information

  1. Vanderbilt University, Nashville, TN, USA

Publication History

  1. Published Online: 15 DEC 2011

Abstract

Among the longest known families of organometallic compounds, those of cobalt display great diversity in their structures and oxidation states. The ligands accommodated in organocobalt compounds range from strong σ-donors such as hydrides and alkyls, to π-acid ligands such as carbonyls and phosphines. The carbonyl cluster compounds of cobalt are numerous and they play a major role in catalytic reactions of enormous industrial importance such as hydroformylation reactions (conversion of alkenes to aldehydes) and Pauson–Khand cycloaddition (production of cyclic ketones). Cobalt is an electron-rich late transition metal, a property reflected throughout its organometallic chemistry. Thus, the carbonyl ‘hydride’ HCo(CO)4 is actually a strong acid and does not have ‘hydridic’ (H) properties. Similarly, cobalt does not complex to any group 15 or 16 heterocycles such as pyridine or thiophene. In contrast, boracycles are good ligands for cobalt in a sandwich complex because an electropositive atom such as boron incorporated in a π-cyclic ring stabilizes the electron-rich central metal. The cyclopentadienyl ligand is found extensively throughout organocobalt chemistry – not only in cobaltocenes, but also in half-sandwich complexes of the type (C5H5)CoL2, where L is CO, alkene, alkyne, or phosphine. The (C5H5)CoL2 complexes are useful in alkyne dimerization and trimerization. Cobaltocene itself ((C5H5)2Co) is easily oxidized to the extraordinarily stable 18-electron cobaltocenium cation, [(C5H5)2Co]+. Cobalt can be incorporated into carborane cages, which have been found to be efficient extractors of radioactive metal ions such as 90Sr and 137Cs in water at low pH. Cobalamins, which consist of a cobalt central atom in a substituted corrin ring, are examples of naturally occurring organometallic compounds, and coenzyme B12 was the first recognized example of a biological organometallic compound. Methylcobalamins play a role in biology, where they are found in microorganisms and can methylate mercury in the environment.

Keywords:

  • carbonyl complex;
  • cluster complex;
  • cobaltocene;
  • hydroformylation;
  • Pauson–Khand cycloaddition