Naked five-coordinate FeIII(NO) porphyrin complexes

Vibrational and reactivity features

Francesco Lanucara, Barbara Chiavarino, Maria Elisa Crestoni, Debora Scuderi, Rajeev K. Sinha, Philippe Maître, Simonetta Fornarini

Research output: Contribution to journalArticle

34 Citations (Scopus)

Abstract

Model ferric heme nitrosyl complexes, [Fe(TPP)(NO)]+ and [Fe(TPFPP)(NO)]+, where TPP is the dianion of 5,10,15,20-tetrakis- phenyl-porphyrin and TPFPP is the dianion of 5,10,15,20-tetrakis- pentafluorophenyl-porphyrin, have been obtained as isolated species by the gas phase reaction of NO with [FeIII(TPP)]+ and [Fe III (TPFPP)]+ ions delivered in the gas phase by electrospray ionization, respectively. The so-formed nitrosyl complexes have been characterized by vibrational spectroscopy also exploiting 15N-isotope substitution in the NO ligand. The characteristic NO stretching frequency is observed at 1825 and 1859 cm-1 for [Fe III(TPP)(NO)]+ and [FeIII(TPFPP)(NO)] + ions, respectively, providing reference values for genuine five-coordinate FeIII(NO) porphyrin complexes differing only for the presence of either phenyl or pentafluorophenyl substituents on the meso positions of the porphyrin ligand. The vibrational assignment is aided by hybrid density functional theory (DFT) calculations of geometry and electronic structure and frequency analysis which clearly support a singlet spin electronic state for both [Fe(TPP)(NO)]+ and [Fe(TPFPP)(NO)]+ complexes. Both TD-DFT and CASSCF calculations suggest that the singlet ground state is best described as FeII(NO+) and that the open-shell AFC bonding scheme contribute for a high-energy excited state. The kinetics of the NO addition reaction in the gas phase are faster for [Fe III(TPFPP)]+ ions by a relatively small factor, though highly reliable because of a direct comparative evaluation. The study was aimed at gaining vibrational and reactivity data on five-coordinate Fe III(NO) porphyrin complexes, typically transient species in solution, ultimately to provide insights into the nature of the Fe(NO) interaction in heme proteins.

Original languageEnglish
Pages (from-to)4445-4452
Number of pages8
JournalInorganic Chemistry
Volume50
Issue number10
DOIs
Publication statusPublished - 16-05-2011

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Porphyrins
porphyrins
reactivity
vapor phases
Gases
Density functional theory
automatic frequency control
density functional theory
ions
ligands
Ions
Ligands
Hemeproteins
Electrospray ionization
Vibrational spectroscopy
Addition reactions
Electronic states
Heme
Excited states
Isotopes

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Lanucara, F., Chiavarino, B., Crestoni, M. E., Scuderi, D., Sinha, R. K., Maître, P., & Fornarini, S. (2011). Naked five-coordinate FeIII(NO) porphyrin complexes: Vibrational and reactivity features. Inorganic Chemistry, 50(10), 4445-4452. https://doi.org/10.1021/ic200073v
Lanucara, Francesco ; Chiavarino, Barbara ; Crestoni, Maria Elisa ; Scuderi, Debora ; Sinha, Rajeev K. ; Maître, Philippe ; Fornarini, Simonetta. / Naked five-coordinate FeIII(NO) porphyrin complexes : Vibrational and reactivity features. In: Inorganic Chemistry. 2011 ; Vol. 50, No. 10. pp. 4445-4452.
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Lanucara, F, Chiavarino, B, Crestoni, ME, Scuderi, D, Sinha, RK, Maître, P & Fornarini, S 2011, 'Naked five-coordinate FeIII(NO) porphyrin complexes: Vibrational and reactivity features', Inorganic Chemistry, vol. 50, no. 10, pp. 4445-4452. https://doi.org/10.1021/ic200073v

Naked five-coordinate FeIII(NO) porphyrin complexes : Vibrational and reactivity features. / Lanucara, Francesco; Chiavarino, Barbara; Crestoni, Maria Elisa; Scuderi, Debora; Sinha, Rajeev K.; Maître, Philippe; Fornarini, Simonetta.

In: Inorganic Chemistry, Vol. 50, No. 10, 16.05.2011, p. 4445-4452.

Research output: Contribution to journalArticle

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T1 - Naked five-coordinate FeIII(NO) porphyrin complexes

T2 - Vibrational and reactivity features

AU - Lanucara, Francesco

AU - Chiavarino, Barbara

AU - Crestoni, Maria Elisa

AU - Scuderi, Debora

AU - Sinha, Rajeev K.

AU - Maître, Philippe

AU - Fornarini, Simonetta

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N2 - Model ferric heme nitrosyl complexes, [Fe(TPP)(NO)]+ and [Fe(TPFPP)(NO)]+, where TPP is the dianion of 5,10,15,20-tetrakis- phenyl-porphyrin and TPFPP is the dianion of 5,10,15,20-tetrakis- pentafluorophenyl-porphyrin, have been obtained as isolated species by the gas phase reaction of NO with [FeIII(TPP)]+ and [Fe III (TPFPP)]+ ions delivered in the gas phase by electrospray ionization, respectively. The so-formed nitrosyl complexes have been characterized by vibrational spectroscopy also exploiting 15N-isotope substitution in the NO ligand. The characteristic NO stretching frequency is observed at 1825 and 1859 cm-1 for [Fe III(TPP)(NO)]+ and [FeIII(TPFPP)(NO)] + ions, respectively, providing reference values for genuine five-coordinate FeIII(NO) porphyrin complexes differing only for the presence of either phenyl or pentafluorophenyl substituents on the meso positions of the porphyrin ligand. The vibrational assignment is aided by hybrid density functional theory (DFT) calculations of geometry and electronic structure and frequency analysis which clearly support a singlet spin electronic state for both [Fe(TPP)(NO)]+ and [Fe(TPFPP)(NO)]+ complexes. Both TD-DFT and CASSCF calculations suggest that the singlet ground state is best described as FeII(NO+) and that the open-shell AFC bonding scheme contribute for a high-energy excited state. The kinetics of the NO addition reaction in the gas phase are faster for [Fe III(TPFPP)]+ ions by a relatively small factor, though highly reliable because of a direct comparative evaluation. The study was aimed at gaining vibrational and reactivity data on five-coordinate Fe III(NO) porphyrin complexes, typically transient species in solution, ultimately to provide insights into the nature of the Fe(NO) interaction in heme proteins.

AB - Model ferric heme nitrosyl complexes, [Fe(TPP)(NO)]+ and [Fe(TPFPP)(NO)]+, where TPP is the dianion of 5,10,15,20-tetrakis- phenyl-porphyrin and TPFPP is the dianion of 5,10,15,20-tetrakis- pentafluorophenyl-porphyrin, have been obtained as isolated species by the gas phase reaction of NO with [FeIII(TPP)]+ and [Fe III (TPFPP)]+ ions delivered in the gas phase by electrospray ionization, respectively. The so-formed nitrosyl complexes have been characterized by vibrational spectroscopy also exploiting 15N-isotope substitution in the NO ligand. The characteristic NO stretching frequency is observed at 1825 and 1859 cm-1 for [Fe III(TPP)(NO)]+ and [FeIII(TPFPP)(NO)] + ions, respectively, providing reference values for genuine five-coordinate FeIII(NO) porphyrin complexes differing only for the presence of either phenyl or pentafluorophenyl substituents on the meso positions of the porphyrin ligand. The vibrational assignment is aided by hybrid density functional theory (DFT) calculations of geometry and electronic structure and frequency analysis which clearly support a singlet spin electronic state for both [Fe(TPP)(NO)]+ and [Fe(TPFPP)(NO)]+ complexes. Both TD-DFT and CASSCF calculations suggest that the singlet ground state is best described as FeII(NO+) and that the open-shell AFC bonding scheme contribute for a high-energy excited state. The kinetics of the NO addition reaction in the gas phase are faster for [Fe III(TPFPP)]+ ions by a relatively small factor, though highly reliable because of a direct comparative evaluation. The study was aimed at gaining vibrational and reactivity data on five-coordinate Fe III(NO) porphyrin complexes, typically transient species in solution, ultimately to provide insights into the nature of the Fe(NO) interaction in heme proteins.

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Lanucara F, Chiavarino B, Crestoni ME, Scuderi D, Sinha RK, Maître P et al. Naked five-coordinate FeIII(NO) porphyrin complexes: Vibrational and reactivity features. Inorganic Chemistry. 2011 May 16;50(10):4445-4452. https://doi.org/10.1021/ic200073v