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Experimental and computational study of a direct O2-coupled Wacker oxidation: water dependence in the absence of Cu salts.

ABSTRACT: The kinetics of the Pd[(-)-sparteine]Cl(2) catalyzed oxidation of decene using oxygen as the sole oxidant have been studied in the absence of copper salts and high [Cl(-)]. Saturation kinetics are observed for [decene] as well as a third order dependence on [water]. A mechanism is proposed involving the dissociation of two chlorides and rate-limiting formation of a three-water hydrogen bridged network and subsequent oxypalladation as supported by computational studies.

SUBMITTER: Anderson BJ

PROVIDER: S-EPMC2929811 | biostudies-literature | 2010 Sep

REPOSITORIES: biostudies-literature

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Experimental and computational study of a direct O2-coupled Wacker oxidation: water dependence in the absence of Cu salts.

Anderson Brian J BJ Keith John A JA Sigman Matthew S MS

Journal of the American Chemical Society 20100901 34

The kinetics of the Pd[(-)-sparteine]Cl(2) catalyzed oxidation of decene using oxygen as the sole oxidant have been studied in the absence of copper salts and high [Cl(-)]. Saturation kinetics are observed for [decene] as well as a third order dependence on [water]. A mechanism is proposed involving the dissociation of two chlorides and rate-limiting formation of a three-water hydrogen bridged network and subsequent oxypalladation as supported by computational studies. ...[more]

PMID: 20687555

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