Linked Life Data

12580614

Source:http://linkedlifedata.com/resource/pubmed/id/12580614

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
7
pubmed:dateCreated
2003-2-12
pubmed:abstractText
Porphyrin architectures bearing a hydrogen-bonding scaffold have been synthesized. The H-bond pendant allows proton-coupled electron transfer (PCET) to be utilized as a vehicle for effecting catalytic O-O bond activation chemistry. Suzuki cross-coupling reactions provide a modular synthetic strategy for the attachment of porphyrins to a rigid xanthene or dibenzofuran pillar bearing the H-bond pendant. The resulting HPX (hanging porphyrin xanthene) and HPD (hanging porphyrin dibenzofuran) systems permit both the orientation and acid-base properties of the hanging H-bonding group to be controlled. Comparative reactivity studies for the catalase-like disproportionation of hydrogen peroxide and the epoxidation of olefins by the HPX and HPD platforms with acid and ester hanging groups reveal that the introduction of a proton-transfer network, properly oriented to a redox-active platform, can orchestrate catalytic O-O bond activation. For the catalase and epoxidation reaction types, a marked reactivity enhancement is observed for the xanthene-bridged platform appended with a pendant carboxylic acid group, establishing that this approach can yield superior catalysts to analogues that do not control both proton and electron inventories.
pubmed:grant
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:month
Feb
pubmed:issn
0002-7863
pubmed:author
pubmed:issnType
Print
pubmed:day
19
pubmed:volume
125
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
1866-76
pubmed:dateRevised
2007-11-14
pubmed:meshHeading
pubmed:year
2003
pubmed:articleTitle
Proton-coupled O-O activation on a redox platform bearing a hydrogen-bonding scaffold.
pubmed:affiliation
Department of Chemistry, 6-335, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139-4307, USA.
pubmed:publicationType
Journal Article, Research Support, U.S. Gov't, P.H.S., Research Support, U.S. Gov't, Non-P.H.S., Research Support, Non-U.S. Gov't