title: Rate and mechanism of the oxidative addition of phenyl iodide to Pd0 ligated by triphenylarsine: evidence for the formation of a T-shaped complex.
abstract: The oxidative addition of phenyl iodide to the palladium(o) generated from [Pd0(dba)2] and n equivalents of AsPh3 (the most efficient catalytic precursor in Stille reactions) proceeds from [(solv)Pd0(AsPh3)2] (solv= solvent). However, the latter is present only in trace concentrations because it is involved in an equilibrium with the major, but nonreactive, complex [Pd0(dba)(AsPh3)2]. As regards the phosphine ligands, dba has a decelerating effect on the rate of the oxidative addition by decreasing the concentration of the reactive species. Relative to PPh3, the effect of AsPh3 is to increase the rate of the oxidative addition of PhI by a factor ten in DMF and seven in THF, independent of the value of n, provided that n > or = 2. In contrast to PPh3, the addition of more than two equivalents of AsPh3 to [Pd0(dba)2] (dba= trans,trans-dibenzylideneacetone) does not affect the kinetics of the oxidative addition because of the very endergonic displacement of dba from [Pd0(dba)(AsPh3)2] to form [Pd0(AsPh3)3]. The complex trans-[PhPdI(AsPh3)2], formed in the oxidative addition, is involved in a slow equilibrium with the T-shaped complex [PhPdI(AsPh3)] after appreciable decomplexation of one AsPh3. Under catalytic conditions, that is, in the presence of a nucleophile, such as CH2=CH-SnBu3 which is able to coordinate to [Pd0(AsPh3)2], a new Pd0 complex is formed: [Pd0(eta2-CH2=CHSnBu3)(AsPh3)2]; however, this complex does not react with PhI. Consequently, CH2=CH-SnBu3 slows down the oxidative addition by decreasing the concentration of the reactive species [(solv)Pd0(AsPh3)2]. This demonstrates that a nucleophile may be not only involved in the transmetallation step, but may also interfere in the kinetics of the oxidative addition step by decreasing the concentration of reactive Pd0.
authors: Ecole Normale Supérieure, Département de Chimie, UMR CNRS 8640, Paris, France. amatore@ens.fr
authors: C
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authors: Amatore
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authors: Bucaille
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authors: Fuxa
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authors: Jutand
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authors: Meyer
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authors: Ndedi Ntepe