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Molecular self-modification: homolog of a manganese laundry bleach catalyst oxidatively transforms its tetradentate ligand into a novel hexadentate derivative

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Abstract

On the basis of mass spectral studies alone, the relatively new manganese complex, Mn(Et2EBC)Cl2 (Et2EBC = 4,11-diethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane), a homolog of the well proven, peroxide-based laundry bleach, Mn(Me2EBC)Cl2, has been reported to undergo a sequence of 2-electron oxidation steps, ultimately converting its ethyl groups into chelated ethoxo and methylene carboxylato groups, [MnIV{(−OCH2CH2)(−O2CCH2)}EBC)](PF6)2. We report here the isolation and characterization of that unusual product, and provide insight into the remarkable catalytic pathway to its formation. At temperatures above 0 °C, oxidation by aqueous H2O2 reliably transforms Mn(Et2EBC)Cl2 into [MnIV{(−OCH2CH2)(−O2CCH2)}EBC)]2+. The experimental data for this intramolecular ethyl group transformation is consistent with oxygen insertion into a methyl C–H moiety of the ethyl group, –NCH2C(–H)H2, by the MnIV–OOH functional group.

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Acknowledgment

Support by the Procter and Gamble Company is deeply appreciated, and we also thank the National Science Foundation Engineering Research Center Grant (EEC-0310689), at the University of Kansas, for partial support. At KU, MS analyses of the manganese(IV) complex under various conditions were performed under the guidance of R. C. Drake, and the crystal structure was determined by Dr Victor Day.

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Authors and Affiliations

  1. Department of Chemistry, The University of Kansas, Lawrence, KS, 66045, USA

    Guochuan Yin, Suparna Baksi Roy, Andrew M. Danby, Victor Day & Daryle H. Busch

  2. The Procter and Gamble Company, Cincinnati, OH, 45202, USA

    John Carter & William M. Scheper

Authors
  1. Guochuan Yin
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  2. Suparna Baksi Roy
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  3. Andrew M. Danby
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  4. Victor Day
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  5. John Carter
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  6. William M. Scheper
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  7. Daryle H. Busch
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Correspondence to Daryle H. Busch.

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Yin, G., Roy, S.B., Danby, A.M. et al. Molecular self-modification: homolog of a manganese laundry bleach catalyst oxidatively transforms its tetradentate ligand into a novel hexadentate derivative. J Incl Phenom Macrocycl Chem 71, 311–318 (2011). https://doi.org/10.1007/s10847-011-9974-x

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  • DOI: https://doi.org/10.1007/s10847-011-9974-x

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