Mechanism of Co-C bond photolysis in the base-on form of methylcobalamin.
A mechanism of Co-C bond photodissociation in the base-on form of the methylcobalamin cofactor (MeCbl) has been investigated employing time-dependent density functional theory (TD-DFT), in which the key step involves singlet radical pair generation from the first electronically excited state (S1). The corresponding potential energy surface of the S1 state was constructed as a function of Co-C and Co-Naxial bond distances, and two possible photodissociation pathways were identified on the basis of energetic grounds. These pathways are distinguished by whether the Co-C bond (path A) or Co-Naxial bond (path B) elongates first. Although the final intermediate of both pathways is the same (namely a ligand field (LF) state responsible for Co-C dissociation), the reaction coordinates associated with paths A and B are different. The photolysis of MeCbl is wavelength-dependent, and present TD-DFT analysis indicates that excitation in the visible α/β band (520 nm) can be associated with path A, whereas excitation in the near-UV region (400 nm) is associated with path B. The possibility of intersystem crossing, and internal conversion to the ground state along path B are also discussed. The mechanism proposed in this study reconciles existing experimental data with previous theoretical calculations addressing the possible involvement of a repulsive triplet state.
Department of Theoretical Chemistry, Institute of Chemistry, University of Silesia , Szkolna 9, PL-40 006 Katowice, Poland.
Piotr
P
Lodowski
Maria
M
Jaworska
Tadeusz
T
Andruniów
Brady D
BD
Garabato
Pawel M
PM
Kozlowski
D002244:Carbon / Q000737:chemistry*; D003035:Cobalt / Q000737:chemistry*; D010782:Photolysis; D011789:Quantum Theory; D014805:Vitamin B 12 / Q000031:analogs & derivatives* / Q000737:chemistry
D003035:Cobalt; D002244:Carbon; C019476:mecobalamin; D014805:Vitamin B 12