Mechanochemical insertion of cobalt into porphyrinoids using Co₂(CO)₈ as a cobalt source

Abstract

The scopes and limits of a solvent-free mechanochemical method to prepare a range of cobalt porphyrinoids is described.

Metal Complexes of Porphyrinoids Containing Nonpyrrolic Heterocycles

“…2,107 Microwave-assisted heating methods and mechanochemical approaches are also available. 108−110 The use of M(0) sources at low temperatures may also offer milder insertion conditions for sensitive porphyrinoids, 85,110 but we are not aware of the utilization of these methods for the formation of metal complexes of pyrrole-modified derivatives. The stable oxidation state of the metal in the metalloporphyrin is then frequently reached by a subsequent (air) oxidation step.…”

“…Therefore, traditional approaches toward the formation of metalloporphyrins frequently employ the reaction of the porphyrin and a metal salt in a (relatively) kinetically labile (often low) oxidation state in a high-boiling donor solvent (pyridine, bp 115 °C; DMF, bp 153 °C; PhCN, bp 191 °C) under reflux conditions over extended periods of time. , Microwave-assisted heating methods and mechanochemical approaches are also available. − The use of M(0) sources at low temperatures may also offer milder insertion conditions for sensitive porphyrinoids, , but we are not aware of the utilization of these methods for the formation of metal complexes of pyrrole-modified derivatives. The stable oxidation state of the metal in the metalloporphyrin is then frequently reached by a subsequent (air) oxidation step. ,, …”

A Bimetallic Porphyrin Metal Organic Framework as Multifunctional Catalysts for CO2 Cycloaddition and Alkyne Hydration

“…A series of characterizations were investigated to verify successful implantation of Co atom. The Fourier transform infrared spectroscopy (Figure 2c) show that the intensity of the asymmetric stretching vibration of the C=O and C−OH group are greatly reduced in Bi−MOF−Co and Bi−MOF compared with Co‐TCPP, which proves the coordination of porphyrin and metallic bismuth [47–49] . As Figure 2 (d) show that a strong symmetric Co−N stretching vibration occurs at around 1000 cm −1 in Bi−MOF−Co, which demonstrates the successful metallization of the porphyrin ring with Co.…”

“…The Fourier transform infrared spectroscopy (Figure 2c) show that the intensity of the asymmetric stretching vibration of the C=O and CÀ OH group are greatly reduced in BiÀ MOFÀ Co and BiÀ MOF compared with Co-TCPP, which proves the coordination of porphyrin and metallic bismuth. [47][48][49] As Figure 2 (d) show that a strong symmetric CoÀ N stretching vibration occurs at around 1000 cm À 1 in BiÀ MOFÀ Co, which demonstrates the successful metallization of the porphyrin ring with Co. The UV-vis spectra show that BiÀ MOF and BiÀ MOFÀ Co have obvious absorption peaks at 414 and 426 nm (Soret band).…”