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  • 1
    Publication Date: 2000-08-11
    Description: Iron species with terminal oxo ligands are implicated as key intermediates in several synthetic and biochemical catalytic cycles. However, there is a dearth of structural information regarding these types of complexes because their instability has precluded isolation under ambient conditions. The isolation and structural characterization of an iron(III) complex with a terminal oxo ligand, derived directly from dioxygen (O2), is reported. A stable structure resulted from placing the oxoiron unit within a synthetic cavity lined with hydrogen-bonding groups. The cavity creates a microenvironment around the iron center that aids in regulating O2 activation and stabilizing the oxoiron unit. These cavities share properties with the active sites of metalloproteins, where function is correlated strongly with site structure.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉MacBeth, C E -- Golombek, A P -- Young, V G Jr -- Yang, C -- Kuczera, K -- Hendrich, M P -- Borovik, A S -- GM49970/GM/NIGMS NIH HHS/ -- GM50781/GM/NIGMS NIH HHS/ -- New York, N.Y. -- Science. 2000 Aug 11;289(5481):938-41.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Department of Chemistry, University of Kansas, Lawrence, KS 66045, USA.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/10937994" target="_blank"〉PubMed〈/a〉
    Keywords: Anthracenes ; Binding Sites ; Chemistry, Physical ; Electron Spin Resonance Spectroscopy ; Ferric Compounds/*chemistry ; Ferrous Compounds/chemistry ; Hydrogen Bonding ; Ligands ; Nitrogen/chemistry ; Oxygen/*chemistry ; Physicochemical Phenomena ; Protons ; Spectroscopy, Fourier Transform Infrared ; Spectroscopy, Mossbauer ; Urea/analogs & derivatives/chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 2
    Publication Date: 1996-03-08
    Description: A key step in dioxygen evolution during photosynthesis is the oxidative generation of the O-O bond from water by a manganese cluster consisting of M2(mu-O)2 units (where M is manganese). The reverse reaction, reductive cleavage of the dioxygen O-O bond, is performed at a variety of dicopper and di-iron active sites in enzymes that catalyze important organic oxidations. Both processes can be envisioned to involve the interconversion of dimetal-dioxygen adducts, M2(O2), and isomers having M2(mu-O)2 cores. The viability of this notion has been demonstrated by the identification of an equilibrium between synthetic complexes having [Cu2(mu-eta2:eta2-O2)]2+ and [Cu2(mu-O)2]2+ cores through kinetic, spectroscopic, and crystallographic studies.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Halfen, J A -- Mahapatra, S -- Wilkinson, E C -- Kaderli, S -- Young, V G Jr -- Que, L Jr -- Zuberbuhler, A D -- Tolman, W B -- GM33162/GM/NIGMS NIH HHS/ -- GM47365/GM/NIGMS NIH HHS/ -- New York, N.Y. -- Science. 1996 Mar 8;271(5254):1397-400.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Department of Chemistry, University of Minnesota, Minneapolis, MN 55455, USA.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/8596910" target="_blank"〉PubMed〈/a〉
    Keywords: Chemistry, Physical ; Copper/*chemistry ; Crystallography, X-Ray ; Heterocyclic Compounds/chemistry ; Organometallic Compounds/chemistry ; Oxidation-Reduction ; Oxygen/*chemistry ; Physicochemical Phenomena ; Spectrophotometry, Ultraviolet ; Spectrum Analysis, Raman ; Temperature
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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