Metal exchange reactions between cadmium protoporphyrin and cobalt and zinc chlorides in acetonitrile and dimethyl sulfoxide

Diphthalocyaninatolanthanum as a New Phthalocyaninato‐Dianion Donor for the Synthesis of Heteroleptic Triple‐Decker Rare Earth Element Crown‐Phthalocyaninato Complexes

“…[10] Magnesium complexes can be transmetallated in acidic media [11] and cadmium ions in porphyrin complexes can be exchanged by cobalt or zinc ions in polar solvents. [12] However, REE exchange was never reported previously. Thus, the reaction described herein is also interesting in relation to the development of the coordination chemistry of tetrapyrrolic compounds.…”

Kinetic control of the transmetalation of labile metalloporphyrins in individual and mixed solvents

“…In polar sol vents with a less pronounced electron donating func tion, the rate of reaction (1) is much higher. The Cd/Zn and Cd/Co transmetalation reactions of blood porphyrins in MeCN (ε = 36, DN = 14.1) are consid erably faster than the same reactions in DMSO (ε = 46.7, DN = 29.8) [16]. This is explained by the lower capability of MeCN to form solvation complexes.…”

“…Likely mechanisms have been suggested for metal ion exchange in labile MPs [6,9,14] same time, the solvent effect as a significant factor in the reaction rate and mechanism [15] has not been properly investigated at the quantitative level. There have been only comparisons of the Cd/Co and Cd/Zn exchange rates in dimethyl sulfoxide (DMSO) and acetonitrile (MeCN) for blood porphyrins [16]. For this reason, we carried out a spectroscopic and kinetic study of the Cd/Cu and Cd/Zn transmetala tion reactions for the cadmium tetraphenylporphine complex (CdTPP, I) in n propanol (n PrOH), N,N dimethylformamide (DMF), DMSO, and MeCN (Table 1) and the same study of the Cd/Cu transmeta lation reaction for CdTPP and cadmium tetraben zoporphine (CdTBP, II) in the DMF-DMSO mixed solvent (Table 2) in wide temperature and concentra tion ranges.…”