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 Buccella, Olga A. Egorova, Yoon Sup Lee, Juhyoun Kwak, David G. Churchill

Research output: Contribution to journalArticle

Abstract

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
JournalPolyhedron
Volume28
Issue number12
DOIs
StatePublished - Aug 5 2009

Fingerprint

Organophosphonates
Porphyrins
nerves
Manganese
porphyrins
manganese
adducts
plots
Ultraviolet spectroscopy
Binding energy
blue shift
Discrete Fourier transforms
red shift
cleavage
binding energy
Metals
Nuclear magnetic resonance
Nerve Agents
corrole
Single crystals

Keywords

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

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Materials Chemistry
  • Physical and Theoretical Chemistry

Cite this

A study of nerve agent model organophosphonate binding with manganese-A2B-corrole and -A2B2-porphyrin systems. / Kim, Kibong; Kim, Inkoo; Maiti, Nilkamal; Kwon, Seong Jung; Buccella, Daniela; Egorova, Olga A.; Lee, Yoon Sup; Kwak, Juhyoun; Churchill, David G.

In: Polyhedron, Vol. 28, No. 12, 05.08.2009, p. 2418-2430.

Research output: Contribution to journalArticle

Kim, K, Kim, I, Maiti, N, Kwon, SJ, Buccella, D, Egorova, OA, Lee, YS, Kwak, J & Churchill, DG 2009, 'A study of nerve agent model organophosphonate binding with manganese-A2B-corrole and -A2B2-porphyrin systems', Polyhedron, vol. 28, no. 12, pp. 2418-2430. https://doi.org/10.1016/j.poly.2009.04.020
Kim, Kibong ; Kim, Inkoo ; Maiti, Nilkamal ; Kwon, Seong Jung ; Buccella, Daniela ; Egorova, Olga A. ; Lee, Yoon Sup ; Kwak, Juhyoun ; Churchill, David G. / A study of nerve agent model organophosphonate binding with manganese-A2B-corrole and -A2B2-porphyrin systems. In: Polyhedron. 2009 ; Vol. 28, No. 12. pp. 2418-2430.
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AU - Buccella, Daniela

AU - Egorova, Olga A.

AU - Lee, Yoon Sup

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N2 - 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.

AB - 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.

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KW - Model nerve agent

KW - Nerve agent sensing

KW - Organophosphonate

KW - trans-AB-porphyrin

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