Effects of peripheral substituents on diastereoselectivity of the fifth ligand-binding to chlorophylls, and nomenclature of the asymmetric axial coordination sites.

ABSTRACT

A preference for one of the two axial ligand-binding sites on the central metal atom of chlorophylls (Chls) and bacteriochlorophylls (BChls) was confirmed. In recently reported crystallographic data on PS2 and LHC2 complexes, there are 42 Chl molecules whose fifth ligands were identified; 33 of 42 molecules bound the fifth ligand at the axial position where the C13(2)-methoxycarbonyl group protrudes (denoting as the 'back'-type isomer). Among 151 (B)Chl a/b molecules found in eight types of (B)Chl proteins including PS2 and LHC2, 124 molecules (82%) are the 'back'-type isomers. Such a statistical selection was observed not only for Chl a but also for Chl b and BChls a/b, indicating that the C3-, C7-, and C8-substituents as well as the macrocyclic pi-conjugates would have little influence on the ligand-binding site. Computational examinations revealed that the energetic gap between the 'back' and its opposite 'face' complexes was inherent to (B)Chls and that the C13(2)-methoxycarbonyl moiety contributed relatively greatly to the diastereomeric preference in the ligand binding. Nomenclature of the two distinguishable sides on chlorophyllous macrocycles, as well as the two asymmetric ligand-binding sites, is also discussed.