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interactions was not observed. In addition, the peaks assignable to an
ion-pair catalyst such as TBA4{Pd(OAc)}[H2SiW10O36Pd2(OAc)2]+
were not observed for the CSI-MS spectrum of TBA-I in 1,2-
dichloroethane. Therefore, an ion-pair catalyst such as {Pd(OAc)+/
[H2SiW10O36Pd2(OAc)2]4−} would not be formed. Detection of TBA-
I by 183W NMR spectroscopy was unsuccessful because the solubility
of TBA-I in 1,2-dichloroethane was low, and the quantity was below
the detection limit of 183W nuclei.
TBA-I·(2f)4, suggesting that the γ-Keggin structure of I is retained
after the hydration.
(31) The CSI-MS spectrum of TBA-I in acetone upon addition of
D2O exhibited the most intense peak (centered at m/z = 3903 + 4)
with isotopic distribution that agrees with the pattern calculated for
TBA5[D4SiW10O38Pd2]+, supporting the elimination of the acetate
ligands by the reaction with water.
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S4. While there were two crystallographically independent anions
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each other (see Figure S2). The structure of IA is shown in Figure 2.
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(27) The supported ruthenium hydroxide catalyst, Ru(OH)x/Al2O3
(Ru: 5 mol% with respect to 1a), was almost inactive under the
present reaction conditions in Table 1. In addition, heterogeneous
nitrile hydration catalyzed by Ru(OH)x/Al2O3 requires a large amount
of water (used as a solvent) and relatively high temperature (>403 K)
to attain high yields of the corresponding amides.4a
(28) DMF and N,N-dimethylacetamide were effective solvents for
hydration of 1a (Table S5); the I-mediated hydration in DMF and
N,N-dimethylacetamide selectively gave 2a without formation of
benzoic acid, while water, dimethyl sulfoxide, and acetone gave 2a in
48, 43, and 38% yields, respectively.
(29) After the recovery of catalyst, 1,2-dimethoxyethane was removed
by evaporation, and 1f, DMF, and water were added again. The
solution was heated at 363 K for 16 h, and no reaction proceeded.
These results ruled out leached palladium species from contributing to
the catalysis.
1
(30) The H NMR and IR spectra of the recovered catalyst showed
the presence of 2f and the absence of acetate ligands. The elemental
analysis of the recovered catalyst revealed that the molar ratio of
Pd:Si:W:2f was 2:1:10:4, respectively. The UV−vis spectrum of the
recovered catalyst approximately agreed with the sum of these of
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dx.doi.org/10.1021/ja3006012 | J. Am. Chem. Soc. 2012, 134, 6425−6433