Synthesis and Spectroscopy of μ-Oxo (O2-)-Bridged Heme/Non-heme Diiron Complexes

Models for the Active Site of Nitric Oxide Reductase

Ian M. Wasser, Constantinus F. Martens, Claudio N. Verani, Eva Rentschler, Hong Wei Huang, Pierre Moenne-Loccoz, Lev N. Zakharov, Arnold L. Rheingold, Kenneth D. Karlin

Research output: Contribution to journalArticle

36 Citations (Scopus)

Abstract

In this paper, we describe the synthesis and study of a series of heme/non-heme Fe-O-Fe′ complexes supported by a porphyrin and the tripodal nitrogen ligand TMPA [TMPA = tris(2-pyridylmethyl)amine]. The complete synthesis of [(6L)Fe-O-Fe(X)]+ (1) (X = OMe- or Cl-, 69:31 ratio), where 6L is the dianion of 5-(o-O-[(N,N-bis(2-pyridylmethyl)-2-(6-methoxyl)pyridinemethanamine)phenyl]-10, 15,20-tris(2,6-difluorophenyl)porphine, is reported. The crystal structure for 1-PF6 reveals an intramolecular heme/non-heme diferric complex bridged by an Fe-O-Fe′ moiety; ∠(Fe-O-Fe′) = 166.7(3)°, and d(Fe⋯Fe′) = 3.556 Å, Crystal data for C70H 57ClF12Fe2N8O3P (1·PF6): triclinic, P1, a = 13.185(3) Å, b = 14,590 (3) Å, c = 16.885(4) Å, α = 104.219(4)°, β = 91.572(4)°, γ = 107.907(4)°, V = 2977.3(11) Å3, Z = 2, T = 150(2) K. Complex 1 (where X = Cl-) is further characterized by UV-vis (λmax = 328, 416 (Soret), 569 nm), 1H NMR (δ 27-24 [TMPA-CH2-], 16.1 [pyrrole-H], 15.2-10.5 [PY-3H, PY-5H], 7.9-7.2 [m- and p-phenyl-H], 6.9-5.8 [PY-4H] ppm), resonance Raman (νas(Fe-O-Fe′) 844 cm-1), and Mössbauer (δFe = 0.47, 0.41 mm/s; ΔEA = 1.59, 0.55 mm/s; 80 K) spectroscopies, MALDI-TOF mass spectrometry (m/z 1202), and SQUID susceptometry (J = - 114,82 cm-1, S = 0). We have also synthesized a series of 3-, 4-, and 5-methyl-substituted as well as selectively deuterated TMPA(Fe′) complexes and condensed these with the hydroxo complex (F8)FeOH or (F8-d8)FeOH to yield "untethered" Fe-O-Fe′ analogues. Along with selective deuteration of the methylene hydrogens in TMPA, complete 1H NMR spectroscopic assignments for 1 have been accomplished. The magnetic properties of several of the untethered complexes and a comparison to those of 1 are also presented. Complex 1 and related species represent good structural and spectroscopic models for the heme/non-heme diiron active site in the enzyme nitric oxide reductase.

Original languageEnglish (US)
Pages (from-to)651-662
Number of pages12
JournalInorganic Chemistry
Volume43
Issue number2
DOIs
StatePublished - Jan 26 2004

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nitric oxide
Heme
Spectroscopy
nuclear magnetic resonance
pyrroles
synthesis
Nuclear magnetic resonance
methylene
porphyrins
spectroscopy
enzymes
amines
Pyrroles
mass spectroscopy
SQUIDs
Porphyrins
analogs
magnetic properties
nitrogen
ligands

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Synthesis and Spectroscopy of μ-Oxo (O2-)-Bridged Heme/Non-heme Diiron Complexes : Models for the Active Site of Nitric Oxide Reductase. / Wasser, Ian M.; Martens, Constantinus F.; Verani, Claudio N.; Rentschler, Eva; Huang, Hong Wei; Moenne-Loccoz, Pierre; Zakharov, Lev N.; Rheingold, Arnold L.; Karlin, Kenneth D.

In: Inorganic Chemistry, Vol. 43, No. 2, 26.01.2004, p. 651-662.

Research output: Contribution to journalArticle

Wasser, IM, Martens, CF, Verani, CN, Rentschler, E, Huang, HW, Moenne-Loccoz, P, Zakharov, LN, Rheingold, AL & Karlin, KD 2004, 'Synthesis and Spectroscopy of μ-Oxo (O2-)-Bridged Heme/Non-heme Diiron Complexes: Models for the Active Site of Nitric Oxide Reductase', Inorganic Chemistry, vol. 43, no. 2, pp. 651-662. https://doi.org/10.1021/ic0348143
Wasser, Ian M. ; Martens, Constantinus F. ; Verani, Claudio N. ; Rentschler, Eva ; Huang, Hong Wei ; Moenne-Loccoz, Pierre ; Zakharov, Lev N. ; Rheingold, Arnold L. ; Karlin, Kenneth D. / Synthesis and Spectroscopy of μ-Oxo (O2-)-Bridged Heme/Non-heme Diiron Complexes : Models for the Active Site of Nitric Oxide Reductase. In: Inorganic Chemistry. 2004 ; Vol. 43, No. 2. pp. 651-662.
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title = "Synthesis and Spectroscopy of μ-Oxo (O2-)-Bridged Heme/Non-heme Diiron Complexes: Models for the Active Site of Nitric Oxide Reductase",
abstract = "In this paper, we describe the synthesis and study of a series of heme/non-heme Fe-O-Fe′ complexes supported by a porphyrin and the tripodal nitrogen ligand TMPA [TMPA = tris(2-pyridylmethyl)amine]. The complete synthesis of [(6L)Fe-O-Fe(X)]+ (1) (X = OMe- or Cl-, 69:31 ratio), where 6L is the dianion of 5-(o-O-[(N,N-bis(2-pyridylmethyl)-2-(6-methoxyl)pyridinemethanamine)phenyl]-10, 15,20-tris(2,6-difluorophenyl)porphine, is reported. The crystal structure for 1-PF6 reveals an intramolecular heme/non-heme diferric complex bridged by an Fe-O-Fe′ moiety; ∠(Fe-O-Fe′) = 166.7(3)°, and d(Fe⋯Fe′) = 3.556 {\AA}, Crystal data for C70H 57ClF12Fe2N8O3P (1·PF6): triclinic, P1, a = 13.185(3) {\AA}, b = 14,590 (3) {\AA}, c = 16.885(4) {\AA}, α = 104.219(4)°, β = 91.572(4)°, γ = 107.907(4)°, V = 2977.3(11) {\AA}3, Z = 2, T = 150(2) K. Complex 1 (where X = Cl-) is further characterized by UV-vis (λmax = 328, 416 (Soret), 569 nm), 1H NMR (δ 27-24 [TMPA-CH2-], 16.1 [pyrrole-H], 15.2-10.5 [PY-3H, PY-5H], 7.9-7.2 [m- and p-phenyl-H], 6.9-5.8 [PY-4H] ppm), resonance Raman (νas(Fe-O-Fe′) 844 cm-1), and M{\"o}ssbauer (δFe = 0.47, 0.41 mm/s; ΔEA = 1.59, 0.55 mm/s; 80 K) spectroscopies, MALDI-TOF mass spectrometry (m/z 1202), and SQUID susceptometry (J = - 114,82 cm-1, S = 0). We have also synthesized a series of 3-, 4-, and 5-methyl-substituted as well as selectively deuterated TMPA(Fe′) complexes and condensed these with the hydroxo complex (F8)FeOH or (F8-d8)FeOH to yield {"}untethered{"} Fe-O-Fe′ analogues. Along with selective deuteration of the methylene hydrogens in TMPA, complete 1H NMR spectroscopic assignments for 1 have been accomplished. The magnetic properties of several of the untethered complexes and a comparison to those of 1 are also presented. Complex 1 and related species represent good structural and spectroscopic models for the heme/non-heme diiron active site in the enzyme nitric oxide reductase.",
author = "Wasser, {Ian M.} and Martens, {Constantinus F.} and Verani, {Claudio N.} and Eva Rentschler and Huang, {Hong Wei} and Pierre Moenne-Loccoz and Zakharov, {Lev N.} and Rheingold, {Arnold L.} and Karlin, {Kenneth D.}",
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TY - JOUR

T1 - Synthesis and Spectroscopy of μ-Oxo (O2-)-Bridged Heme/Non-heme Diiron Complexes

T2 - Models for the Active Site of Nitric Oxide Reductase

AU - Wasser, Ian M.

AU - Martens, Constantinus F.

AU - Verani, Claudio N.

AU - Rentschler, Eva

AU - Huang, Hong Wei

AU - Moenne-Loccoz, Pierre

AU - Zakharov, Lev N.

AU - Rheingold, Arnold L.

AU - Karlin, Kenneth D.

PY - 2004/1/26

Y1 - 2004/1/26

N2 - In this paper, we describe the synthesis and study of a series of heme/non-heme Fe-O-Fe′ complexes supported by a porphyrin and the tripodal nitrogen ligand TMPA [TMPA = tris(2-pyridylmethyl)amine]. The complete synthesis of [(6L)Fe-O-Fe(X)]+ (1) (X = OMe- or Cl-, 69:31 ratio), where 6L is the dianion of 5-(o-O-[(N,N-bis(2-pyridylmethyl)-2-(6-methoxyl)pyridinemethanamine)phenyl]-10, 15,20-tris(2,6-difluorophenyl)porphine, is reported. The crystal structure for 1-PF6 reveals an intramolecular heme/non-heme diferric complex bridged by an Fe-O-Fe′ moiety; ∠(Fe-O-Fe′) = 166.7(3)°, and d(Fe⋯Fe′) = 3.556 Å, Crystal data for C70H 57ClF12Fe2N8O3P (1·PF6): triclinic, P1, a = 13.185(3) Å, b = 14,590 (3) Å, c = 16.885(4) Å, α = 104.219(4)°, β = 91.572(4)°, γ = 107.907(4)°, V = 2977.3(11) Å3, Z = 2, T = 150(2) K. Complex 1 (where X = Cl-) is further characterized by UV-vis (λmax = 328, 416 (Soret), 569 nm), 1H NMR (δ 27-24 [TMPA-CH2-], 16.1 [pyrrole-H], 15.2-10.5 [PY-3H, PY-5H], 7.9-7.2 [m- and p-phenyl-H], 6.9-5.8 [PY-4H] ppm), resonance Raman (νas(Fe-O-Fe′) 844 cm-1), and Mössbauer (δFe = 0.47, 0.41 mm/s; ΔEA = 1.59, 0.55 mm/s; 80 K) spectroscopies, MALDI-TOF mass spectrometry (m/z 1202), and SQUID susceptometry (J = - 114,82 cm-1, S = 0). We have also synthesized a series of 3-, 4-, and 5-methyl-substituted as well as selectively deuterated TMPA(Fe′) complexes and condensed these with the hydroxo complex (F8)FeOH or (F8-d8)FeOH to yield "untethered" Fe-O-Fe′ analogues. Along with selective deuteration of the methylene hydrogens in TMPA, complete 1H NMR spectroscopic assignments for 1 have been accomplished. The magnetic properties of several of the untethered complexes and a comparison to those of 1 are also presented. Complex 1 and related species represent good structural and spectroscopic models for the heme/non-heme diiron active site in the enzyme nitric oxide reductase.

AB - In this paper, we describe the synthesis and study of a series of heme/non-heme Fe-O-Fe′ complexes supported by a porphyrin and the tripodal nitrogen ligand TMPA [TMPA = tris(2-pyridylmethyl)amine]. The complete synthesis of [(6L)Fe-O-Fe(X)]+ (1) (X = OMe- or Cl-, 69:31 ratio), where 6L is the dianion of 5-(o-O-[(N,N-bis(2-pyridylmethyl)-2-(6-methoxyl)pyridinemethanamine)phenyl]-10, 15,20-tris(2,6-difluorophenyl)porphine, is reported. The crystal structure for 1-PF6 reveals an intramolecular heme/non-heme diferric complex bridged by an Fe-O-Fe′ moiety; ∠(Fe-O-Fe′) = 166.7(3)°, and d(Fe⋯Fe′) = 3.556 Å, Crystal data for C70H 57ClF12Fe2N8O3P (1·PF6): triclinic, P1, a = 13.185(3) Å, b = 14,590 (3) Å, c = 16.885(4) Å, α = 104.219(4)°, β = 91.572(4)°, γ = 107.907(4)°, V = 2977.3(11) Å3, Z = 2, T = 150(2) K. Complex 1 (where X = Cl-) is further characterized by UV-vis (λmax = 328, 416 (Soret), 569 nm), 1H NMR (δ 27-24 [TMPA-CH2-], 16.1 [pyrrole-H], 15.2-10.5 [PY-3H, PY-5H], 7.9-7.2 [m- and p-phenyl-H], 6.9-5.8 [PY-4H] ppm), resonance Raman (νas(Fe-O-Fe′) 844 cm-1), and Mössbauer (δFe = 0.47, 0.41 mm/s; ΔEA = 1.59, 0.55 mm/s; 80 K) spectroscopies, MALDI-TOF mass spectrometry (m/z 1202), and SQUID susceptometry (J = - 114,82 cm-1, S = 0). We have also synthesized a series of 3-, 4-, and 5-methyl-substituted as well as selectively deuterated TMPA(Fe′) complexes and condensed these with the hydroxo complex (F8)FeOH or (F8-d8)FeOH to yield "untethered" Fe-O-Fe′ analogues. Along with selective deuteration of the methylene hydrogens in TMPA, complete 1H NMR spectroscopic assignments for 1 have been accomplished. The magnetic properties of several of the untethered complexes and a comparison to those of 1 are also presented. Complex 1 and related species represent good structural and spectroscopic models for the heme/non-heme diiron active site in the enzyme nitric oxide reductase.

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