Direct Structural and Chemical Characterization of the Photolytic Intermediates of Methylcobalamin Using Time-Resolved X-ray Absorption Spectroscopy

Ganesh Subramanian, Xiaoyi Zhang, Gerdenis Kodis, Qingyu Kong, Cunming Liu, Andrew Chizmeshya, Uwe Weierstall, John Spence

Research output: Contribution to journalArticle

4 Scopus citations

Abstract

Cobalt-carbon bond cleavage is crucial to most natural and synthetic applications of the cobalamin class of compounds, and here we present the first direct electronic and geometric structural characteristics of intermediates formed following photoexcitation of methylcobalamin (MeCbl) using time-resolved X-ray absorption spectroscopy (XAS). We catch transients corresponding to two intermediates, in the hundreds of picoseconds and a few microseconds. Highlights of the picosecond intermediate, which is reduced in comparison to the ground state, are elongation of the upper axial Co-C bond and relaxation of the corrin ring. This is not so with the recombining photocleaved products captured at a few microseconds, where the Co-C bond almost (yet not entirely) reverts to its ground state configuration and a substantially elongated lower axial Co-NIm bond is observed. The reduced cobalt site here confirms formation of methyl radical as the photoproduct.

Original languageEnglish (US)
Pages (from-to)1542-1546
Number of pages5
JournalJournal of Physical Chemistry Letters
Volume9
Issue number7
DOIs
StatePublished - Apr 5 2018

ASJC Scopus subject areas

  • Materials Science(all)

Fingerprint Dive into the research topics of 'Direct Structural and Chemical Characterization of the Photolytic Intermediates of Methylcobalamin Using Time-Resolved X-ray Absorption Spectroscopy'. Together they form a unique fingerprint.

Cite this