53513-20-5

Upstream product

• 36158-67-5 CoI(CO)3(P(C₆H₅)3) 
• 16331-64-9 ethanolate 
• 45581-66-6 benzyl oxide ion 
• 475597-25-2 Na[Co(CO)3(η2-fullerene-60)] 
• 603-35-0 triphenylphosphine 
• 475597-31-0 ((C₆H₅)3P)2N⁽¹⁺⁾*Co(CO)3C₆₀^(1-)=[((C₆H₅)3P)2N]Co(CO)3C₆₀ 
• 3315-60-4 methanolate 

Downstream Products

• 14911-28-5 Co₂(CO)6{P(C₄H₉-n)3}2 
• 118400-48-9 Co₂(CO)6(P(C₆H₅)3)(P(C₄H₉)3) 

Relevant academic research and scientific papers

Anionic fullerene-60 complexes of manganese(-I), cobalt(-I), and rhenium(-I): Thermal and photoinduced electron transfer processes between metal carbonylate anions and C60

Thermal and photochemical reactions of THF solutions of the carbonylate salts A[Mn(CO)5], A[Co(CO)4], and A[Re(CO)5] (A = Na, PPN) with suspensions of C60 result in electron transfer to give [C60]- and the transient 17-electron, metal-centered radicals Mn(CO)5, Co(CO)4, and Re(CO)5, respectively. However, the ensuing secondary processes vary significantly, depending on the metal and the reaction conditions. With manganese and rhenium, self-coupling of M(CO)5 (M = Mn, Re) to give the metal-metal bonded dimers M2(CO)10 and coupling of M(CO)5 with [C60]- to give the η2-C60 complexes A[Mn(CO)4(η2-C60)] both occur under thermal and photochemical conditions. In contrast, the photochemical processes ultimately result also in complete homolysis of the dimers and regeneration of the metal-centered radicals, which then combine with fullende ion [C60]- still remaining in solution to form more of the η2-C60 complexes. In the case of cobalt, no Co2(CO)8 is formed, but the η2-C60 complex [Co(CO)3(η2-C60]- is produced. While the latter is thermally unstable in refluxing THF, undergoing decarbonylation to the previously reported mixed metal fullende compound NaCoC60·3THF, it is thermally stable under photochemical conditions at room temperature. Spectroscopic evidence suggests that much of the negative charge in [Mn(CO)4(η2-C60)]- is delocalized onto the fullerene ligand; as a result, the η2-C60-Mn bond is unusually strong and the complex [Mn(CO)4(η2-C60)]- is very stable, exhibiting little of the chemistry associated with either neutral η2-C60 complexes or the analogous [Mn(CO)5]-.

(Alkoxycarbonyl)- and [(aryloxy)carbonyl]cobalt carbonyls

(Alkoxycarbonyl)cobalt tetracarbonyls (1) were synthesized from Co2(CO)8 in THF and from ICo(CO)4 by the reaction with the corresponding alkali-metal alkoxides in saturated hydrocarbons using crown ethers as solid/liquid phase-transfer catalysts. Both 1 and, for the first time, [(aryloxy)carbonyl]cobalt tetracarbonyls (2) were obtained in a homogeneous system containing ICo(CO)4 and alkali-metal alkoxides or phenoxides, respectively, in THF. Tertiary phosphine derivatives of 1 and 2 were also prepared. The formation of complexes 1 and 2 proceeds through the ionic intermediates [ICo(COOR)(CO)3]- which were characterized by their infrared spectra. Analogous ionic species [Co(COOR)2(CO)3]- are formed from the reaction of complexes 1 and RO. [(Allyloxy)carbonyl]cobalt tetracarbonyl shows thermal decarboxylation at 20°C yielding (η3-C3H5)Co(CO)3 and CO2.