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rdf:type
lifeskim:mentions
pubmed:issue
7
pubmed:dateCreated
2005-3-28
pubmed:abstractText
The synthesis and characterization of a new oxorhenium(V) compound is reported; it is [MeReO(edt)(bpym)], 8, where edt = 1,2-ethanedithiolate and bpym = 2,2'-bipyrimidine. Compound 8 was characterized by NMR spectroscopy and single-crystal X-ray analysis. It exists as a six-coordinate Re(V) compound comparable to the previously known [MeReO(edt)(bpy)] and [MeReO(mtp)(bpy)]. Compound 8 catalyzes the oxygen-atom-transfer reaction PicO + PZ3 --> Pic + Z3PO, whereas the other two do not. The kinetics of this reaction with catalyst 8 follows the rate law -d[PicO]/dt = k[8][PicO]/(1 + c[PZ3]). With different phosphines, the rate law has the same k value, 4.17 L mol(-1) s(-1), but different c values. For tritolylphosphine, c = 67.5 L mol(-1) in benzene at 25 degrees C. A mechanism has been proposed to account for these findings. The data establish that an open coordination site on rhenium is necessary for oxygen-atom-transfer reactions.
pubmed:language
eng
pubmed:journal
pubmed:status
PubMed-not-MEDLINE
pubmed:month
Apr
pubmed:issn
0020-1669
pubmed:author
pubmed:issnType
Print
pubmed:day
4
pubmed:volume
44
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
2560-5
pubmed:year
2005
pubmed:articleTitle
New oxorhenium(V) compound for catalyzed oxygen atom transfer from picoline N-oxide to triarylphosphines.
pubmed:affiliation
Ames Laboratory and Department of Chemistry, Iowa State University, Ames, Iowa 50011, USA.
pubmed:publicationType
Journal Article