Synthesis and spectroscopy of μ-oxo (O2-)-bridged heme/non-heme diiron complexes:: Models for the active site of nitric oxide reductase

Autoren

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

DOI

10.1021/ic0348143

eISSN

1520-510X

ISSN

0020-1669

Ausgabe der Veröffentlichung

2

Zeitschrift

Inorganic Chemistry

Sprache

en

Online publication date

2003

Paginierung

651 - 662

Datum der Veröffentlichung

2004

Status

Published

Herausgeber

American Chemical Society (ACS)

Herausgeber URL

http://dx.doi.org/10.1021/ic0348143

Datum der Datenerfassung

2023

Titel

Synthesis and Spectroscopy of μ-Oxo (O<sup>2</sup><sup>-</sup>)-Bridged Heme/Non-heme Diiron Complexes: Models for the Active Site of Nitric Oxide Reductase

Ausgabe der Zeitschrift

43

Data source: Crossref

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 [((6)L)Fe-O-Fe(X)](+) (1) (X = OMe(-) or Cl(-), 69:31 ratio), where (6)L 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.PF(6) reveals an intramolecular heme/non-heme diferric complex bridged by an Fe-O-Fe' moiety; 90 degree angle (Fe-O-Fe') = 166.7(3) degrees, and d(Fe.Fe') = 3.556 A. Crystal data for C(70)H(57)ClF(12)Fe(2)N(8)O(3)P (1.PF(6)): triclinic, Ponemacr;, a = 13.185(3) A, b = 14.590 (3) A, c = 16.885(4) A, alpha = 104.219(4) degrees, beta = 91.572(4) degrees, gamma = 107.907(4) degrees, V = 2977.3(11) A(3), Z = 2, T = 150(2) K. Complex 1 (where X = Cl(-)) is further characterized by UV-vis (lambda(max) = 328, 416 (Soret), 569 nm), (1)H NMR (delta 27-24 [TMPA -CH(2)-], 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 (nu(as)(Fe-O-Fe') 844 cm(-)(1)), and Mössbauer (delta(Fe) = 0.47, 0.41 mm/s; deltaE(A) = 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 (F(8))FeOH or (F(8)-d(8))FeOH to yield "untethered" Fe-O-Fe' analogues. Along with selective deuteration of the methylene hydrogens in TMPA, complete (1)H 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.

Addresses

Department of Chemistry, Johns Hopkins University, Charles and 34th Streets, Baltimore, Maryland 21218, USA.

Autoren

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

DOI

10.1021/ic0348143

eISSN

1520-510X

Externe Identifier

PubMed Identifier: 14731027

Funding acknowledgements

NIGMS NIH HHS: GM60353
NIGMS NIH HHS: GM18865

Open access

false

ISSN

0020-1669

Ausgabe der Veröffentlichung

2

Zeitschrift

Inorganic chemistry

Schlüsselwörter

Iron
Iron Radioisotopes
Oxidoreductases
Nonheme Iron Proteins
Indicators and Reagents
Crystallography, X-Ray
Magnetic Resonance Spectroscopy
Spectroscopy, Mossbauer
Spectrum Analysis, Raman
Binding Sites
Protein Conformation
Magnetics
Models, Molecular

Sprache

eng

Medium

Print

Paginierung

651 - 662

Datum der Veröffentlichung

2004

Status

Published

Datum der Datenerfassung

2004

Titel

Synthesis and spectroscopy of micro-oxo (O(2)(-))-bridged heme/non-heme diiron complexes: models for the active site of nitric oxide reductase.

Sub types

Research Support, U.S. Gov't, P.H.S.
Journal Article

Ausgabe der Zeitschrift

43

Data source: Europe PubMed Central

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 [((6)L)Fe-O-Fe(X)](+) (1) (X = OMe(-) or Cl(-), 69:31 ratio), where (6)L 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.PF(6) reveals an intramolecular heme/non-heme diferric complex bridged by an Fe-O-Fe' moiety; 90 degree angle (Fe-O-Fe') = 166.7(3) degrees, and d(Fe.Fe') = 3.556 A. Crystal data for C(70)H(57)ClF(12)Fe(2)N(8)O(3)P (1.PF(6)): triclinic, Ponemacr;, a = 13.185(3) A, b = 14.590 (3) A, c = 16.885(4) A, alpha = 104.219(4) degrees, beta = 91.572(4) degrees, gamma = 107.907(4) degrees, V = 2977.3(11) A(3), Z = 2, T = 150(2) K. Complex 1 (where X = Cl(-)) is further characterized by UV-vis (lambda(max) = 328, 416 (Soret), 569 nm), (1)H NMR (delta 27-24 [TMPA -CH(2)-], 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 (nu(as)(Fe-O-Fe') 844 cm(-)(1)), and Mössbauer (delta(Fe) = 0.47, 0.41 mm/s; deltaE(A) = 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 (F(8))FeOH or (F(8)-d(8))FeOH to yield "untethered" Fe-O-Fe' analogues. Along with selective deuteration of the methylene hydrogens in TMPA, complete (1)H 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.

Autoren

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

Autoren-URL

https://www.ncbi.nlm.nih.gov/pubmed/14731027

DOI

10.1021/ic0348143

Funding acknowledgements

NIGMS NIH HHS: GM18865
NIGMS NIH HHS: GM60353

ISSN

0020-1669

Ausgabe der Veröffentlichung

2

Zeitschrift

Inorg Chem

Schlüsselwörter

Binding Sites
Crystallography, X-Ray
Indicators and Reagents
Iron
Iron Radioisotopes
Magnetic Resonance Spectroscopy
Magnetics
Models, Molecular
Nonheme Iron Proteins
Oxidoreductases
Protein Conformation
Spectroscopy, Mossbauer
Spectrum Analysis, Raman

Sprache

eng

Country

United States

Paginierung

651 - 662

Datum der Veröffentlichung

2004

Status

Published

Datum, an dem der Datensatz öffentlich gemacht wurde

2004

Titel

Synthesis and spectroscopy of micro-oxo (O(2)(-))-bridged heme/non-heme diiron complexes: models for the active site of nitric oxide reductase.

Sub types

Journal Article
Research Support, U.S. Gov't, P.H.S.

Ausgabe der Zeitschrift

43

Data source: PubMed

Synthesis and spectroscopy of μ-oxo (O2-)-bridged heme/non-heme diiron complexes:: Models for the active site of nitric oxide reductase

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