Several [Fe(II)2(N-EtHPTB)(μ-O2X)](2+) complexes (1·O2X) have been synthesized, where N-EtHPTB is the anion of N,N,N'N'-tetrakis(2-benzimidazolylmethyl)-2-hydroxy-1,3-diaminopropane and O2X is an oxyanion bridge. Crystal structures reveal five-coordinate (μ-alkoxo)diiron(II) cores. These diiron(II) complexes react with O2 at low temperatures in CH2Cl2 (-90 °C) to form blue-green O2 adducts that are best described as triply bridged (μ-η(1):η(1)-peroxo)diiron(III) species (2·O2X). With one exception, all 2·O2X intermediates convert irreversibly to doubly bridged, blue (μ-η(1):η(1)-peroxo)diiron(III) species (3·O2X). Where possible, 2·O2X and 3·O2X intermediates were characterized using resonance Raman spectroscopy, showing respective νO-O values of ∼850 and ∼900 cm(-1). How the steric and electronic properties of O2X affect conversion of 2·O2X to 3·O2X was examined. Stopped-flow analysis reveals that oxygenation kinetics of 1·O2X is unaffected by the nature of O2X, and for the first time, the benzoate analog of 2·O2X (2·O2CPh) is observed.
Several [Fe(II)2(N-EtHPTB)(μ-n class="Chemical">O2X)](2+) complexes (1·O2X) have been synthesized, where N-EtHPTB is the anion of N,N,N'N'-tetrakis(2-benzimidazolylmethyl)-2-hydroxy-1,3-diaminopropane and O2X is an oxyanion bridge. Crystal structures reveal five-coordinate (μ-alkoxo)diiron(II) cores. These diiron(II) complexes react with O2 at low temperatures in CH2Cl2 (-90 °C) to form blue-green O2 adducts that are best described as triply bridged (μ-η(1):η(1)-peroxo)diiron(III) species (2·O2X). With one exception, all 2·O2X intermediates convert irreversibly to doubly bridged, blue (μ-η(1):η(1)-peroxo)diiron(III) species (3·O2X). Where possible, 2·O2X and 3·O2X intermediates were characterized using resonance Raman spectroscopy, showing respective νO-O values of ∼850 and ∼900 cm(-1). How the steric and electronic properties of O2X affect conversion of 2·O2X to 3·O2X was examined. Stopped-flow analysis reveals that oxygenation kinetics of 1·O2X is unaffected by the nature of O2X, and for the first time, the benzoate analog of 2·O2X (2·O2CPh) is observed.
Authors: Danny Yun; Ricardo García-Serres; Brandon M Chicalese; Young H An; Boi Hanh Huynh; J Martin Bollinger Journal: Biochemistry Date: 2007-01-27 Impact factor: 3.162
Authors: Andrew L. Feig; Michael Becker; Siegfried Schindler; Rudi van Eldik; Stephen J. Lippard Journal: Inorg Chem Date: 1996-04-24 Impact factor: 5.165
Authors: Maarten Merkx; Daniel A. Kopp; Matthew H. Sazinsky; Jessica L. Blazyk; Jens Müller; Stephen J. Lippard Journal: Angew Chem Int Ed Engl Date: 2001-08-03 Impact factor: 15.336
Authors: Miquel Costas; Clyde W Cady; Sergey V Kryatov; Manabendra Ray; Meghan J Ryan; Elena V Rybak-Akimova; Lawrence Que Journal: Inorg Chem Date: 2003-11-17 Impact factor: 5.165
Authors: Effie C Kisgeropoulos; Yunqiao J Gan; Samuel M Greer; Joseph M Hazel; Hannah S Shafaat Journal: J Am Chem Soc Date: 2022-07-05 Impact factor: 16.383