Journal
DALTON TRANSACTIONS
Volume 39, Issue 44, Pages 10626-10630Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c0dt00628a
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Funding
- Egyptian Ministry of Higher Education
- NSF [CHE-0848397]
- Department of Energy, Office of Biological and Environmental Research (BER)
- National Institutes of Health, National Center for Research Resources (NCRR)
- Biomedical Technology Program (BTP)
- National Institute of General Medical Sciences (NIGMS)
- NATIONAL CENTER FOR RESEARCH RESOURCES [P41RR001209] Funding Source: NIH RePORTER
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The X-ray structures of three new crystals of nitroxylcobalamin (NOCbl) have been determined. Unlike our earlier reported structure in which NOCbl was partially oxidized (L. Hannibal, C. A. Smith, D. W. Jacobsen and N. E. Brasch, Angew. Chem., Int. Ed. 2007, 46, 5140), the O atom of the nitroxyl ligand is located in a single position with a N=O bond distance of 1.12 1.14 angstrom, consistent with a double bond. The Co-N-O angle is in the 118.9-120.3 angstrom range. The alpha-axial Co-N(dimethylbenzimidazole) (Co-NB3) bond distance is a remarkable 2.32-2.35 angstrom in length, similar to 0.1 angstrom longer than that reported for all other cobalamin structures. The change in the Gibbs free energy for the base-on/base-off equilibrium now correlates extremely well with the Co-NB3 bond distance, as observed for other cobalamins.
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