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Solution, Crystal and in Silico Structures of the Organometallic Vitamin B 12 ‐Derivative Acetylcobalamin and of its Novel Rhodium‐Analogue Acetylrhodibalamin

Wiedemair, Markus, Kieninger, Christoph, Wurst, Klaus, Podewitz, Maren, Deery, Evelyne, Paxhia, Michael D., Warren, Martin J., Kräutler, Bernhard (2023) Solution, Crystal and in Silico Structures of the Organometallic Vitamin B 12 ‐Derivative Acetylcobalamin and of its Novel Rhodium‐Analogue Acetylrhodibalamin. Helvetica Chimica Acta, 106 (2). Article Number e202200158. ISSN 1522-2675. (doi:10.1002/hlca.202200158) (KAR id:99669)


The natural vitamin B12‐derivatives are intriguing complexes of cobalt that entrap the metal within the strikingly skewed and ring‐contracted corrin ligand. Here, we describe the synthesis of the Rh(III)‐corrin acetylrhodibalamin (AcRhbl) from biotechnologically produced metal‐free hydrogenobyric acid and analyze the effect of the replacement of the cobalt‐center of the organometallic vitamin B12‐derivative acetylcobalamin (AcCbl) with its group‐IX homologue rhodium, to give AcRhbl. The structures of AcCbl and AcRhbl were thoroughly analyzed in aqueous solution, in crystals and by in silico methods, in order to gain detailed insights into the structural adaptations to the two homologous metals. Indeed, the common, nucleotide‐appended corrin‐ligand in these two metal corrins features extensive structural similarity. Thus, the rhodium‐corrin AcRhbl joins the small group of B12‐mimics classified as ‘antivitamins B12’, isostructural metal analogues of the natural cobalt‐corrins that hold significant potential in biological and biomedical applications as selective inhibitors of key cellular processes.

Item Type: Article
DOI/Identification number: 10.1002/hlca.202200158
Additional information: For the purpose of open access, the author(s) has applied a Creative Commons Attribution (CC BY) licence to any Author Accepted Manuscript version arising.
Uncontrolled keywords: antivitamin B12, cobalt, corrin, density functional calculations, organometallic chemistry, Salmonella, rhodium, transition metals, X-ray diffraction
Subjects: Q Science
Q Science > QH Natural history > QH301 Biology
Q Science > QR Microbiology
Divisions: Divisions > Division of Natural Sciences > Biosciences
Funders: FWF Austrian Science Fund (
Biotechnology and Biological Sciences Research Council (
SWORD Depositor: JISC Publications Router
Depositing User: JISC Publications Router
Date Deposited: 17 Feb 2023 15:53 UTC
Last Modified: 20 Nov 2023 15:38 UTC
Resource URI: (The current URI for this page, for reference purposes)

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