Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 27, Issue 25, Pages 7252-7264Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202004589
Keywords
bond dissociation energy; cobinamide; mass spectrometry; vitamins
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Funding
- ETH Zurich
- Swiss National Science Foundation
- Deutsche Forschungsgemeinschaft [SPP 1807]
- Austrian Science Fund [P-28892, P-33059]
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The study synthesized a new class of organometallic cationic aryl-cobinamides and determined their stereo-structure using NMR spectra. Gas-phase bond dissociation energies of different isomers were measured by ESI-MS threshold CID experiments, revealing significant contributions of non-bonded interactions in aryl-cobinamides.
Aryl-cobalamins are a new class of organometallic structural mimics of vitamin B-12 designed as potential 'antivitamins B-12'. Here, the first cationic aryl-cobinamides are described, which were synthesized using the newly developed diaryl-iodonium method. The aryl-cobinamides were obtained as pairs of organometallic coordination isomers, the stereo-structure of which was unambiguously assigned based on homo- and heteronuclear NMR spectra. The availability of isomers with axial attachment of the aryl group, either at the 'beta' or at the 'alpha' face of the cobalt-center allowed for an unprecedented comparison of the organometallic reactivity of such pairs. The homolytic gas-phase bond dissociation energies (BDEs) of the coordination-isomeric phenyl- and 4-ethylphenyl-cobinamides were determined by ESI-MS threshold CID experiments, furnishing (Co-Csp2 )-BDEs of 38.4 and 40.6 kcal mol(-1), respectively, for the two beta-isomers, and the larger BDEs of 46.6 and 43.8 kcal mol(-1) for the corresponding alpha-isomers. Surprisingly, the observed (Co-Csp2 )-BDEs of the Co-beta-aryl-cobinamides were smaller than the (Co-Csp3 )-BDE of Co-beta-methyl-cobinamide. DFT studies and the magnitudes of the experimental (Co-Csp2 )-BDEs revealed relevant contributions of non-bonded interactions in aryl-cobinamides, notably steric strain between the aryl and the cobalt-corrin moieties and non-bonded interactions with and among the peripheral sidechains.
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