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Replacement of the Cobalt Center of Vitamin B 12 by Nickel: Nibalamin and Nibyric Acid Prepared from Metal‐Free B 12 Ligands Hydrogenobalamin and Hydrogenobyric Acid

Kieninger, Christoph, Wurst, Klaus, Podewitz, Maren, Stanley, Maria, Deery, Evelyne, Lawrence, Andrew D., Liedl, Klaus R., Warren, Martin J., Kräutler, Bernhard (2020) Replacement of the Cobalt Center of Vitamin B 12 by Nickel: Nibalamin and Nibyric Acid Prepared from Metal‐Free B 12 Ligands Hydrogenobalamin and Hydrogenobyric Acid. Angewandte Chemie International Edition, . ISSN 1433-7851. (doi:10.1002/anie.202008407) (KAR id:82762)

Abstract

The (formal) replacement of Co in cobalamin (Cbl) by NiII generates nibalamin (Nibl), a new transition‐metal analogue of vitamin B12. Described here is Nibl, synthesized by incorporation of a NiII ion into the metal‐free B12 ligand hydrogenobalamin (Hbl), itself prepared from hydrogenobyric acid (Hby). The related NiII corrin nibyric acid (Niby) was similarly synthesized from Hby, the metal‐free cobyric acid ligand. The solution structures of Hbl, and Niby and Nibl, were characterized by spectroscopic studies. Hbl features two inner protons bound at N2 and N4 of the corrin ligand, as discovered in Hby. X‐ray analysis of Niby shows the structural adaptation of the corrin ligand to NiII ions and the coordination behavior of NiII. The diamagnetic Niby and Nibl, and corresponding isoelectronic CoI corrins, were deduced to be isostructural. Nibl is a structural mimic of four‐coordinate base‐off Cbls, as verified by its ability to act as a strong inhibitor of bacterial adenosyltransferase.

Item Type: Article
DOI/Identification number: 10.1002/anie.202008407
Uncontrolled keywords: cobalamins, porphyrinoids, transition metals, crystal structures, vitamins
Subjects: Q Science
Divisions: Divisions > Division of Natural Sciences > Biosciences
Depositing User: Martin Warren
Date Deposited: 04 Sep 2020 12:58 UTC
Last Modified: 01 Oct 2020 08:24 UTC
Resource URI: https://kar.kent.ac.uk/id/eprint/82762 (The current URI for this page, for reference purposes)

University of Kent Author Information

Stanley, Maria.

Creator's ORCID:
CReDIT Contributor Roles:

Deery, Evelyne.

Creator's ORCID: https://orcid.org/0000-0002-8189-678X
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Lawrence, Andrew D..

Creator's ORCID: https://orcid.org/0000-0002-5853-5409
CReDIT Contributor Roles:

Warren, Martin J..

Creator's ORCID: https://orcid.org/0000-0002-6028-6456
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