Document Detail

Charged tags as probes for analyzing organometallic intermediates and monitoring cross-coupling reactions by electrospray-ionization mass spectrometry.
MedLine Citation:
PMID:  20836538     Owner:  NLM     Status:  MEDLINE    
Organic iodides bearing a cationic quaternary ammonium group at a remote position react with zerovalent Pd complexes, Zn, or In leading to a C-I bond insertion. The resulting charge-tagged organometallics can be detected by electrospray-ionization mass spectrometry, which provides detailed information on their stoichiometry, oxidation state, and coordination sphere. The properties of the observed organopalladium and -zinc intermediates largely agree with previous findings, whereas the organoindium species show a surprisingly high tendency to form ate complexes. Magnesium also undergoes insertion into the C-I bond of the charge-tagged organic iodides, but instead of the expected organomagnesium intermediates only the corresponding hydrolysis products could be detected in the diluted solutions. Electrospray-ionization mass spectrometry can also be used to study the reactivity of the charge-tagged species, as was demonstrated for a Pd-catalyzed Negishi cross-coupling reaction. The presented approach permits a straightforward identification of the rate-limiting step and the determination of the corresponding second-order rate constant.
Matthias A Schade; Julia E Fleckenstein; Paul Knochel; Konrad Koszinowski
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Publication Detail:
Type:  Journal Article; Research Support, Non-U.S. Gov't    
Journal Detail:
Title:  The Journal of organic chemistry     Volume:  75     ISSN:  1520-6904     ISO Abbreviation:  J. Org. Chem.     Publication Date:  2010 Oct 
Date Detail:
Created Date:  2010-10-08     Completed Date:  2011-01-25     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  2985193R     Medline TA:  J Org Chem     Country:  United States    
Other Details:
Languages:  eng     Pagination:  6848-57     Citation Subset:  IM    
Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstr. 5-13, 81377 München, Germany.
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MeSH Terms
Iodobenzenes / chemistry*
Molecular Structure
Organometallic Compounds / chemical synthesis,  chemistry*
Palladium / chemistry*
Quaternary Ammonium Compounds / chemistry*
Spectrometry, Mass, Electrospray Ionization
Reg. No./Substance:
0/Iodobenzenes; 0/Organometallic Compounds; 0/Quaternary Ammonium Compounds; 7440-05-3/Palladium

From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine

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