Co(4-norbornyl)4 is a rare example of a low-spin tetrahedral complex and a rare case of an organocobalt(V) derivative.
Most fundamental are the cobalt complexes with only alkyl ligands. Examples include Co(4-norbornyl)4 and its cation.[3]
Alkylcobalt is represented by vitamin B12 and related enzymes. In methylcobalamin the ligand is a methyl group, which is electrophilic. in vitamin B12, the alkyl ligand is an adenosyl group. Related to vitamin B12 are cobalt porphyrins, dimethylglyoximates, and related complexes of Schiff base ligands. These synthetic compounds also form alkyl derivatives that undergo diverse reactions reminiscent of the biological processes. The weak cobalt(III)-carbon bond in vitamin B12 analogues can be exploited in a type of Cobalt mediated radical polymerization of acrylic and vinyl esters (e.g. vinyl acetate), acrylic acid, and acrylonitrile.[4]
Carbonyl complexes
Dicobalt octacarbonyl is produced by the carbonylation of cobalt salts. It and its phosphine derivatives are among the most widely used organocobalt compounds. Heating Co2(CO)8 gives Co4(CO)12. Very elaborate cobalt-carbonyl clusters have been prepared starting from these complexes. Heating cobalt carbonyl with bromoform gives methylidynetricobaltnonacarbonyl. Dicobalt octacarbonyl also reacts with alkynes to give dicobalt hexacarbonyl acetylene complexes with the formula Co2(CO)6(C2R2). Because they can be removed later, the cobalt carbonyl centers function as a protective group for the alkyne. In the Nicholas reaction an alkyne group is also protected and at the same time the alpha-carbon position is activated for nucleophilic substitution.
Cp, allyl, and alkene compounds
Sandwich compounds
Co(1,5-cyclooctadiene)(cyclooctenyl).
Organocobalt compounds are known with alkene, allyl, diene, and Cp ligands. A famous sandwich compound is cobaltocene, a rare example of low-spin Co(II) complex. This 19-electron metallocene is used as a reducing agent and as a source of CpCo. Other sandwich compounds are CoCp(C6Me6) and Co(C6Me6)2, with 20 electrons and 21 electrons, respectively. Reduction of anhydrous cobalt(II) chloride with sodium in the presence of cyclooctadiene gives Co(cyclooctadiene)(cyclooctenyl), a synthetically versatile reagent.[5]
The half-sandwich compounds of the type CpCoL2 have been well-investigated (L = CO, alkene). The complexes CpCo(C2H4)2 and CpCo(cod) catalyze alkyne trimerisation,[6] which has been applied to the synthesis of a variety of complex structures.[7]
Mechanism proposed for trimerisation of alkyne to give arenes.
Applications
Mechanism of cobalt-catalyzed hydroformylation. The process begins with dissociation of CO from cobalt tetracarbonyl hydride to give the 16-electron species (step 1). Subsequent binding of alkene gives an 18e species (step 2). In step 3, the olefin inserts to give the 16e alkyl tricarbonyl. Coordination of another equivalent of CO give alkyl tetracarbonyl (step 4). Migratory insertion of CO gives the 16e acyl in step 5. In step 6, oxidative addition of hydrogen gives a dihydrido complex, which in step 7 releases aldehyde by reductive elimination. Step 8 is unproductive and reversible.
Dicobalt octacarbonyl is used commercially for hydroformylation of alkenes. A key intermediate is cobalt tetracarbonyl hydride (HCo(CO)4). Processes involving cobalt are practiced commercially mainly for the production of C7-C14 alcohols used for the production of surfactants.[10][11] Many hydroformylations have switched from cobalt-based processes to rhodium-based processes, despite the great expense of that metal. Replacing H2 by water or an alcohol, the reaction product is a carboxylic acid or an ester. An example of this reaction type is the conversion of butadiene to adipic acid. Cobalt catalysts (together with iron) are relevant in the Fischer–Tropsch process in which it is assumed that organocobalt intermediates form.
Cobalt complexes have been applies to the synthesis of pyridine derivatives starting from alkynes and nitriles.
Aspirational applications
Although really only dicobalt octacarbonyl has achieved commercial success, many reports have appeared promising applications.[12][13][14] Often these ventures are motivated by the use of "earth abundant" catalysts.[15]
↑ Byrne, Erin K.; Theopold, Klaus H. (1987-02-01). "Redox chemistry of tetrakis(1-norbornyl)cobalt. Synthesis and Characterization of a Cobalt(V) Alkyl and Self-Exchange Rate of a Co(III)/Co(IV) Couple". Journal of the American Chemical Society. 109 (4): 1282–1283. doi:10.1021/ja00238a066. ISSN0002-7863.
↑ Gosser, L. W.; Cushing, M. A. Jr. (1977). "Π-Cyclooctenyl-π-L,5-Cycloocta-Dienecobalt". π-Cyclooctenyl-π-1,5-cyclooctadienecobalt. Inorganic Syntheses. Vol.17. pp.112–15. doi:10.1002/9780470132487.ch32. ISBN978-0-470-13248-7.
↑ Cobalt-Catalyzed Cyclotrimerization of Alkynes: The Answer to the Puzzle of Parallel Reaction Pathways Nicolas Agenet, Vincent Gandon, K. Peter C. Vollhardt, Max Malacria, Corinne Aubert J. Am. Chem. Soc.; 2007; 129(28) pp 8860 - 8871; (Article) doi:10.1021/ja072208r
↑ Hebrard, Frédéric; Kalck, Philippe (2009). "Cobalt-Catalyzed Hydroformylation of Alkenes: Generation and Recycling of the Carbonyl Species, and Catalytic Cycle". Chemical Reviews. 109 (9): 4272–4282. doi:10.1021/cr8002533. PMID19572688.
↑ Boy Cornils, Wolfgang A. Herrmann, Chi-Huey Wong, Horst Werner Zanthoff: Catalysis from A to Z: A Concise Encyclopedia, 2408Seiten, Verlag Wiley-VCH Verlag GmbH & Co. KGaA, (2012), ISBN3-527-33307-X.
↑ Liu, Weiping; Sahoo, Basudev; Junge, Kathrin; Beller, Matthias (2018). "Cobalt Complexes as an Emerging Class of Catalysts for Homogeneous Hydrogenations". Accounts of Chemical Research. 51 (8): 1858–1869. doi:10.1021/acs.accounts.8b00262. PMID30091891. S2CID51954703.
↑ Guo, Jun; Cheng, Zhaoyang; Chen, Jianhui; Chen, Xu; Lu, Zhan (2021). "Iron- and Cobalt-Catalyzed Asymmetric Hydrofunctionalization of Alkenes and Alkynes". Accounts of Chemical Research. 54 (11): 2701–2716. doi:10.1021/acs.accounts.1c00212. PMID34011145. S2CID234792059.
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