Phosphoryl oxygen sensing capabilities of manganese 5,15-di(aryl)-10-(3-vinylphenyl)corrole complexes

INOR 660

Kibong Kim, kkb826@kaist.ac.kr, Nilkamal Maiti, nkmaiti@rediffmail.com, and David G. Churchill, dchurchill@kaist.ac.kr. Department of Chemistry and School of Molecular Science (BK 21), Korea Advanced Institute of Science and Technology (KAIST), 373-1 Guseong-dong, Yuseong-gu, Daejeon, 305-701, South Korea
Nerve agents such as VX and Sarin (1995 Tokyo city subway attack) are acutely toxic, and new agent sensing modes are actively being researched. We have been investigating the interactions between the central metal ions of manganese corroles and organophosphonate nerve agent mimics via extensive UV-vis measurements. The substrates bind to manganese via the phosphoryl oxygen; titrations with (CH3CH2O)2P=O(C3H6NMe2), (C4H9O)2P=O(Me), (C2H5O)2P=O(Me), (CH3C(O)CH2)P=O(OC2H5)2, Ph3P=O, as well as pyridine and acetonitrile give rise to distinct changes in characteristic metallocorrole UV-vis absorption bands. The complexes herein are generated from 5,15-di(aryl)-10-(3-vinylphenyl)corrole where aryl = thienyl, pentafluorphenyl. We have also been studying how these and related metallocorrole derivatives participate in oxygen atom transfer reactions. The vinyl group in the ligand is meant as a latent attachment point.