2015
DOI: 10.1002/chem.201406258
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Concerning the Deactivation of Cobalt(III)‐Based Porphyrin and Salen Catalysts in Epoxide/CO2 Copolymerization

Abstract: Functioning as active catalysts for propylene oxide (PO) and carbon dioxide copolymerization, cobalt(III)-based salen and porphyrin complexes have drawn great attention owing to their readily modifiable nature and promising catalytic behavior, such as high selectivity for the copolymer formation and good regioselectivity with respect to the polymer microstructure. Both cobalt(III)-salen and porphyrin catalysts have been found to undergo reduction reactions to their corresponding catalytically inactive cobalt(I… Show more

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Cited by 29 publications
(24 citation statements)
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“…17 Moreover, Co-based salen and porphyrin catalysts were observed to deactivate during CO 2 /propylene oxide copolymerisation through reduction of the cobalt centre. 2,82 Zinc β-diiminates represent another well-studied class of homogeneous catalysts that has found widespread application in polymerisations of CO 2 with a broad range of epoxides (Fig. 3, 3).…”
Section: Homogeneous Catalytic Systemsmentioning
confidence: 99%
“…17 Moreover, Co-based salen and porphyrin catalysts were observed to deactivate during CO 2 /propylene oxide copolymerisation through reduction of the cobalt centre. 2,82 Zinc β-diiminates represent another well-studied class of homogeneous catalysts that has found widespread application in polymerisations of CO 2 with a broad range of epoxides (Fig. 3, 3).…”
Section: Homogeneous Catalytic Systemsmentioning
confidence: 99%
“…Upon metalation, the Q band of the protonated free base porphyrins of (2H) 2 ‐1 at 670 nm disappeared and Co(II) to Co(III) porphyrins oxidation was shown by a large red shift of the Soret band from 413 to 433 nm (see Figure S10–11). Cobalt(III)Cl meso ‐tetraphenylporphyrin CoCl‐TPP , used as reference catalyst, was obtained following the same procedure (Scheme 1b) and its characterisation was in accordance with literature data [18f] …”
Section: Resultsmentioning
confidence: 96%
“…Cage (CoCl) 2 ‐1 was prepared from the previously reported free‐base porphyrin cage (2H) 2 ‐1 , [19] according to slight modifications of published procedures describing the metalation of free‐base porphyrins with cobalt(III) ions [18d,f, 20] (Scheme 1a).…”
Section: Resultsmentioning
confidence: 99%
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“…The stronger electron‐donating nature of the dimethylamino groups could increase the contribution of the radical cationic species [Co II (NMe 2 ‐salcy)] +• . Since divalent Co is inactive for PPC synthesis, this could be the reason for the low reactivity of 7 .…”
Section: Resultsmentioning
confidence: 99%