TY - JOUR
T1 - Oxygen transfer from sulfoxides
T2 - Oxidation of alkylarenes catalyzed by a polyoxomolybdate, [PMo12O40]3-
AU - Khenkin, Alexander M.
AU - Neumann, Ronny
PY - 2002/4/24
Y1 - 2002/4/24
N2 - The polyoxomolydate of the Keggin structure, PMo12O403-, catalyzes, under anaerobic conditions, oxygen transfer from sulfoxides to alkylarenes such as xanthene and diphenylmethane to yield xanthen-9-one and benzophenone, respectively. With use of 17O and 18O labeled phenylmethylsulfoxide it was shown that the sulfoxide is complexed by the polyoxometalate and the oxygen is transferred from the sulfoxide to the alkylarene. There is a good correlation between the reaction rate and the heterolytic benzylic C-H bond energy indicating a hydride transfer reaction from the alkylarene to the polyoxometalate-sulfoxide complex. In the case of triphenylmethane the resulting carbocation reacts to yield 9-phenylfluorene as the major product. The reaction kinetics supports such a reaction pathway.
AB - The polyoxomolydate of the Keggin structure, PMo12O403-, catalyzes, under anaerobic conditions, oxygen transfer from sulfoxides to alkylarenes such as xanthene and diphenylmethane to yield xanthen-9-one and benzophenone, respectively. With use of 17O and 18O labeled phenylmethylsulfoxide it was shown that the sulfoxide is complexed by the polyoxometalate and the oxygen is transferred from the sulfoxide to the alkylarene. There is a good correlation between the reaction rate and the heterolytic benzylic C-H bond energy indicating a hydride transfer reaction from the alkylarene to the polyoxometalate-sulfoxide complex. In the case of triphenylmethane the resulting carbocation reacts to yield 9-phenylfluorene as the major product. The reaction kinetics supports such a reaction pathway.
UR - http://www.scopus.com/inward/record.url?scp=0037165678&partnerID=8YFLogxK
U2 - 10.1021/ja0178721
DO - 10.1021/ja0178721
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C2 - 11960434
AN - SCOPUS:0037165678
SN - 0002-7863
VL - 124
SP - 4198
EP - 4199
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 16
ER -