A study of nerve agent model organophosphonate binding with manganese-A2B-corrole and -A2B2-porphyrin systems

Kibong Kim, Inkoo Kim, Nilkamal Maiti, Seong Jung Kwon, Daniela Bucella, Olga A. Egorova, Yoon Sup Lee, Juhyoun Kwak, David G. Churchill

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Herein the synthesis and binding studies of novel trans-A2B-corrole and trans-A2B2-porphyrin derivatives are presented in comparing manganese(III)-organophosphonate (OP) binding (e.g., Mn+ ← O{double bond, long}PR(OR)2) capabilities. H3(PFP-VC) [PFP-VC = 5,15-di(pentafluorophenyl)-10-(3-vinylphenyl)corrolate] was synthesized by way of literature procedures and was characterized by a variety of 2-D NMR spectroscopic techniques and single-crystal X-ray diffraction. These compounds represent the first example of 3-vinyl-phenyl-containing meso-substituted corroles or porphyrins. Mn(PFP-VC) (3) was treated separately with (CH3CH2O)2P{double bond, long}O(C3H6NMe2), (C4H9O)2P{double bond, long}O(Me), (C2H5O)2P{double bond, long}O(CH2COCH3), (CH3CH2O)2P{double bond, long}O(Me), to give 1:1 adducts, as determined by UV-Vis spectroscopy (Job Plot), giving a red shift; Ph3P{double bond, long}O, was also found to bind, but very weakly. The trans-A2B2-porphyrin analogue Mn(PFP-VP) (4) was also prepared by way of a literature procedure; related binding studies gave 1:1 organophosphonate-Mn(PFP-VP) adducts (Job Plot). A clean blue shift occurred for the Mn-porphyrins at higher organophosphonate loadings (Ka values: 6.7 (0.9)-11.9 (0.4) M-1). DFT geometry optimizations of O{double bond, long}P(OMe)2Me binding and formal Mn-O or P-O cleavage products in the unsubstituted neutral Mn-corrolato and -porphyrinato systems with a range of metal-based spin states revealed greatest stability in formal phosphoryl oxygen binding (energies: 11-13 kcal/mol) for the Mn-corrole (singlet); the Mn-porphyrin (sextet) was also quite stable.

Original languageEnglish (US)
Pages (from-to)2418-2430
Number of pages13
Issue number12
StatePublished - Aug 5 2009


  • AB-corrole
  • Binding study
  • Cyclic voltammetry
  • Manganese
  • Model nerve agent
  • Nerve agent sensing
  • Organophosphonate
  • UV-Vis titrations
  • trans-AB-porphyrin

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry


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