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Kinetic and Mechanistic Study of the H‐Transfer Reduction of Dimethyl Itaconate by a Rh/TPPTS Catalyst under Biphasic Conditions: Evidence for a Rhodametallacycle Intermediate
Author(s) -
Tanchoux Nathalie,
Bellefon Claude de
Publication year - 2000
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200007)2000:7<1495::aid-ejic1495>3.0.co;2-j
Subject(s) - tppts , chemistry , catalysis , sodium formate , formate , kinetic energy , hydrogen , photochemistry , reaction mechanism , kinetics , catalytic cycle , inorganic chemistry , medicinal chemistry , combinatorial chemistry , organic chemistry , rhodium , hydroformylation , physics , quantum mechanics
The H‐transfer reduction of dimethyl itaconate under biphasic catalysis using sodium formate/water as the hydrogen source with a Rh/TPPTS complex was studied. Labelling experiments reveal that the reduction proceeds through a 1,3‐hydrogen addition. Kinetic studies allow us to propose a catalytic cycle going through a rhodametallacyclobutane intermediate with a rate‐determining step involving sodium formate. A formal kinetic rate law was then derived from this mechanism which accounts for the results. This work evidences the switch between the mechanism of diacid reduction and that of the corresponding esters.