Title: On the Configuration Resulting from Oxidative Addition of RX to Pd(PPh<sub>3</sub>)<sub>4</sub> and the Mechanism of the <i>cis</i>-to-<i>trans</i> Isomerization of [PdRX(PPh<sub>3</sub>)<sub>2</sub>] Complexes (R = Aryl, X = Halide)
Abstract: The oxidative addition of RI to Pd(0) and further cis-to-trans isomerization, which are involved in the Stille reaction and other Pd-catalyzed syntheses, have been studied. C6Cl2F3I (1, C6Cl2F3 = 3,5-dichlorotrifluorophenyl) adds to Pd(PPh3)4 in THF at room temperature giving cis-[Pd(C6Cl2F3)I(PPh3)2] (2), which could be isolated before isomerization to the more stable trans-[Pd(C6Cl2F3)I(PPh3)2] (3). A 19F NMR kinetic study of the isomerization of 2 in THF at 322.6 K reveals a first-order law riso = kiso[2], with kiso = f + g[2]0 + (h + i[2]0)/([PPh3] + j) (f = (1.66 ± 0.03) × 10-4 s-1, g = (2.5 ± 0.2) × 10-3 mol-1 L s-1, h = (1.3 ± 0.7) × 10-8 mol L-1 s-1, i = (4 ± 2) × 10-7 s-1, and j = (1.4 ± 0.7) × 10-5 mol L-1). A four-pathway mechanism accounts for these results: Two are assigned to the associative replacements of PPh3 coordinated to 2 by an iodide ligand of I−[Pd] (I−[Pd] = 2 or 3), both THF-assisted (coefficient h) or direct (coefficient i), leading to a monoiodide-bridged intermediate cis-{Pd(C6Cl2F3)I(PPh3)(μ-I)-[Pd]}. The later rearranges via terminal-for-bridging iodide exchange to trans-{Pd(C6Cl2F3)I(PPh3)(μ-I)]-[Pd]}, which is finally cleaved by PPh3 yielding complex 3. The other two concurrent pathways are assigned to the isomerization via two consecutive Berry pseudorotations in the pentacoordinated species derived from 2 by coordination of THF (coefficient f) or I−[Pd] (coefficient g). The apparent activation entropy associated with kiso is negative (ΔS⧧ = −21 ± 3 J K-1 mol-1), in agreement with the proposed bimolecular mechanisms.
Publication Year: 1998
Publication Date: 1998-02-10
Language: en
Type: article
Indexed In: ['crossref']
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Cited By Count: 170
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