Complex formation between NADH model compounds and metalloporphyrins

Shunichi Fukuzumi, Yuji Kondo, Seiji Mochizuki, Toshio Tanaka

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42 Scopus citations


Various NADH model compounds, 1-(X-benzyl)-1,4-dihydronicotinamide (X-BNAH: X = 4-MeO, 4-Me, H, 4-Cl2, and 2,4-Cl2) and 10-methyl-9,10-dihydroacridine (AcrH2), form complexes with metalloporphyrins (FeTPPCIO4, FeTPPCI, MnTPPCIO4, and ZnTPP; TPP: tetraphenylporphyrin) in dichloromethane or chloroform. For the BNAH-ZnTPP system, the stoicheiometry of the complex formation is 1:1 with the formation constant K = 50 dm3 mol-1 in dichloromethane at 298 K. In the BNAH-MTPPCIO4 system (M = Fe and Mn), both 1:1 and 2:1 complexes are formed depending on the ratio of BNAH to MTPPCIO4. The formation constant becomes larger as the donor ability of NADH model compounds increases. Both the five-co-ordinate FeTPP(BNAH)+ and six-co-ordinate FeTPP(BNAH)2+ complexes are high-spin (S = 5/2) species. The complex formation between the reduced metalloporphyrin (FeTPP and MnTPP) with BNAH was also investigated by the technique of cyclic voltammetry, which revealed that the reduced iron porphyrin FeTPP also forms a bis-co-ordination complex with BNAH, but the MnTPP forms only a mono-ligand adduct with BNAH. NADH model compounds are shown to act as two-electron donors in the electron-transfer reactions with FeTPPCIO4 in the presence of oxygen in acetonitrile, when the overall rates are determined by the rates of electron transfer from X-BNAH to FeTPP+ together with the competition between the back electron transfer from FeTPP to X-BNAH+. and the deprotonation of BNAH+..

Original languageEnglish
Pages (from-to)1753-1761
Number of pages9
JournalJournal of the Chemical Society. Perkin Transactions 2
Issue number11
StatePublished - 1989


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