The unusual, slow redox properties of Cu, Ni, and Rh cobalamins

Rubinson, Kenneth A.; Čaja, Josip; Hurst, Roger W.; Itabashi, Eiki; Kenyhercz, Thomas M.; Heineman, William R.; Mark, Harry B.

doi:10.1039/c39800000047

Cited by 9 publications

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“…This is inferred from the fact that Co(I) is isoelectronic with Ni(II), which when chelated with corrin does not appear to bind any ligands in the fifth or sixth position. 22 Another interesting conclusion derives from the relative energies of the [Co(II)]cobalamin in base-on and base-off forms. The base-off form is more stable by about 3 kcal/mol.…”

Section: Methodsmentioning

confidence: 99%

The chemistry of [Co]cobalamins: equilibrium constants and energies of formation of species in aqueous solution

Rubinson¹,

Parekh²,

Itabashi³

et al. 1983

Inorg. Chem.

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Cross reactions between nickel(III) peptides and nickel(II) peptides in aqueous solution are used to evaluate the self-exchange rate constants, fcu, of these species. The values of ku for 16 different peptide complexes vary with their structure but can be classified into the following groups: triply deprotonated peptides (1.2 X 105 M'1 s'1), except for H_3G5 (4.2 X 104 M"1 s'1), and doubly deprotonated peptides (1.3 x 104 M'1 s'1). The cross reactions are catalyzed by bridging ligands 5 X 10'3 M Br". The order of enhanced reactivity is Br*

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Section: Methodsmentioning

confidence: 99%

The chemistry of [Co]cobalamins: equilibrium constants and energies of formation of species in aqueous solution

Rubinson¹,

Parekh²,

Itabashi³

et al. 1983

Inorg. Chem.

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Iridium Complexes of 2,2′‐Bidipyrrins

Bröring

Brandt

Tejero

2005

Zeitschrift anorg allge chemie

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The reaction of [{Ir(cod)(μ‐Cl)}2] and K2CO3 or of [{Ir(cod)(μ‐OMe)}2] alone with the non‐natural tetrapyrrole 2,2′‐bidipyrrin (H2BDP) yields, depending on the stoichiometry, the mononuclear complex [Ir(cod)(HBDP)] or the homodinuclear complex [{Ir(cod)}2(BDP)]. Both complexes react readily with carbon monoxide to yield the species [Ir(CO)2(HBDP)] and [{Ir(CO)2}2(BDP)], respectively. The results from NMR spectroscopy and X‐ray diffraction reveal different conformations for the tetrapyrrolic ligand in both complexes. The reaction of [{Ir(coe)2(μ‐Cl)}2] with H2BDP proceeds differently and yields the macrocyclic [4e−,2H+]‐oxidized product [IrCl2(9‐Meic)] (9‐Meic = monoanion of 9‐methyl‐9,10‐isocorrole), which can be addressed as an iridium analog of cobalamin.

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General Redox Processes and Reactions between Two Complexes

Twigg¹

1983

Volume 1: Mechanisms of Inorganic and Organometallic Reactions

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The unusual, slow redox properties of Cu, Ni, and Rh cobalamins

Abstract: The rates of the redox processes for several metal cobalhmin complexes are virtually zero which suggests that the use of other complexes to model the redox properties of vitamin B,, compounds is questionable.

Cited by 9 publications

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The chemistry of [Co]cobalamins: equilibrium constants and energies of formation of species in aqueous solution

The chemistry of [Co]cobalamins: equilibrium constants and energies of formation of species in aqueous solution

Iridium Complexes of 2,2′‐Bidipyrrins

General Redox Processes and Reactions between Two Complexes

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