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Primary Amine Stabilization of a Dicopper(lll) Bis(µ-oxo) Species: Modeling the Ligation in pMMO.

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Title: Primary Amine Stabilization of a Dicopper(lll) Bis(µ-oxo) Species: Modeling the Ligation in pMMO.
Authors: Citek, Cooper1, Bo-Lin Lin1, Phelps, Tim E.2, Wasinger, Erik C.2, Stack, T. Daniel P.1 stack@stanford.edu
Source: Journal of the American Chemical Society. 10/15/2014, Vol. 136 Issue 41, p14405-14408. 4p. 2 Color Photographs, 3 Diagrams, 1 Chart.
Subjects: Copper compounds synthesis, Amines, Propene, Polysaccharides, Methane monooxygenase
Abstract: Here we report the formation of the first examples of dicopper(III) bis(µ-oxo) complexes ligated by the primary amines, propylenediamine, and N,N,-dimethyl propylenediamine. Stabilization of these new compounds is effected at —125 °C by “core capture”— introduction of exogenous ligand to a preformed dicopper(lll) bis(µ-oxo) complex supported by the peralkylated tetramethyl propylenediamine. Primary amine ligation in these compounds matches the single primary amine coordination of the putative active site of particulate methane monooxygenase (pMMO) and polysaccharide monooxygenase. Reactivity studies presented here show primary amine ligated cores are competent oxidants, capable of activating C—H bonds by an H-atom abstraction mechanism. Trends in spectroscopy, structure, and reactivity provide hints to the potential role of primary amine ligation in pMMO: increased substrate accessibility to the redox active orbitals of the Cu2O2 core and greater stabilization of the oxidant without attenuation of oxidizing power. [ABSTRACT FROM AUTHOR]
Copyright of Journal of the American Chemical Society is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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Header DbId: egs
DbLabel: Engineering Source
An: 99124294
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PubType: Academic Journal
PubTypeId: academicJournal
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  Data: Primary Amine Stabilization of a Dicopper(lll) Bis(µ-oxo) Species: Modeling the Ligation in pMMO.
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  Data: <searchLink fieldCode="JN" term="%22Journal+of+the+American+Chemical+Society%22">Journal of the American Chemical Society</searchLink>. 10/15/2014, Vol. 136 Issue 41, p14405-14408. 4p. 2 Color Photographs, 3 Diagrams, 1 Chart.
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  Data: <searchLink fieldCode="DE" term="%22Copper+compounds+synthesis%22">Copper compounds synthesis</searchLink><br /><searchLink fieldCode="DE" term="%22Amines%22">Amines</searchLink><br /><searchLink fieldCode="DE" term="%22Propene%22">Propene</searchLink><br /><searchLink fieldCode="DE" term="%22Polysaccharides%22">Polysaccharides</searchLink><br /><searchLink fieldCode="DE" term="%22Methane+monooxygenase%22">Methane monooxygenase</searchLink>
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  Data: Here we report the formation of the first examples of dicopper(III) bis(µ-oxo) complexes ligated by the primary amines, propylenediamine, and N,N,-dimethyl propylenediamine. Stabilization of these new compounds is effected at —125 °C by “core capture”— introduction of exogenous ligand to a preformed dicopper(lll) bis(µ-oxo) complex supported by the peralkylated tetramethyl propylenediamine. Primary amine ligation in these compounds matches the single primary amine coordination of the putative active site of particulate methane monooxygenase (pMMO) and polysaccharide monooxygenase. Reactivity studies presented here show primary amine ligated cores are competent oxidants, capable of activating C—H bonds by an H-atom abstraction mechanism. Trends in spectroscopy, structure, and reactivity provide hints to the potential role of primary amine ligation in pMMO: increased substrate accessibility to the redox active orbitals of the Cu2O2 core and greater stabilization of the oxidant without attenuation of oxidizing power. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
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  Data: <i>Copyright of Journal of the American Chemical Society is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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        Value: 10.1021/ja508630d
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        Text: English
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      – SubjectFull: Copper compounds synthesis
        Type: general
      – SubjectFull: Amines
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      – SubjectFull: Propene
        Type: general
      – SubjectFull: Polysaccharides
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      – SubjectFull: Methane monooxygenase
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      – TitleFull: Primary Amine Stabilization of a Dicopper(lll) Bis(µ-oxo) Species: Modeling the Ligation in pMMO.
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              Text: 10/15/2014
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