Document Detail


Coordination chemistry and reactivity of a cupric hydroperoxide species featuring a proximal H-bonding substituent.
MedLine Citation:
PMID:  23153187     Owner:  NLM     Status:  MEDLINE    
Abstract/OtherAbstract:
At -90 °C in acetone, a stable hydroperoxo complex [(BA)Cu(II)OOH](+) (2) (BA, a tetradentate N(4) ligand possessing a pendant -N(H)CH(2)C(6)H(5) group) is generated by reacting [(BA)Cu(II)(CH(3)COCH(3))](2+) with only 1 equiv of H(2)O(2)/Et(3)N. The exceptional stability of 2 is ascribed to internal H-bonding. Species 2 is also generated in a manner not previously known in copper chemistry, by adding 1.5 equiv of H(2)O(2) (no base) to the cuprous complex [(BA)Cu(I)](+). The broad implications for this finding are discussed. Species 2 slowly converts to a μ-1,2-peroxodicopper(II) analogue (3) characterized by UV-vis and resonance Raman spectroscopies. Unlike a close analogue not possessing internal H-bonding, 2 affords no oxidative reactivity with internal or external substrates. However, 2 can be protonated to release H(2)O(2), but only with HClO(4), while 1 equiv Et(3)N restores 2.
Authors:
Sunghee Kim; Claudio Saracini; Maxime A Siegler; Natalia Drichko; Kenneth D Karlin
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Publication Detail:
Type:  Journal Article; Research Support, N.I.H., Extramural     Date:  2012-11-15
Journal Detail:
Title:  Inorganic chemistry     Volume:  51     ISSN:  1520-510X     ISO Abbreviation:  Inorg Chem     Publication Date:  2012 Dec 
Date Detail:
Created Date:  2012-12-03     Completed Date:  2013-05-13     Revised Date:  2013-12-05    
Medline Journal Info:
Nlm Unique ID:  0366543     Medline TA:  Inorg Chem     Country:  United States    
Other Details:
Languages:  eng     Pagination:  12603-5     Citation Subset:  IM    
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MeSH Terms
Descriptor/Qualifier:
Coordination Complexes / chemical synthesis,  chemistry*
Copper / chemistry*
Hydrogen Bonding
Hydrogen Peroxide / chemistry*
Models, Molecular
Molecular Structure
Grant Support
ID/Acronym/Agency:
R01 GM028962/GM/NIGMS NIH HHS; R01 GM28962/GM/NIGMS NIH HHS
Chemical
Reg. No./Substance:
0/Coordination Complexes; 789U1901C5/Copper; BBX060AN9V/Hydrogen Peroxide
Comments/Corrections

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