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The alternative is a pendant carbonium, unreactive toward the necessarily zero-valent Pd neighbor.
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One possible artifact is radiation damage. There is no evidence for radiation damage in the present case, and our analysis does not rest on radiation damage as the source of the structural conclusions from solution EXAFS data.
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We have shown with ONIOM calculations on 1′ that the phenyl groups do not perturb the first coordination sphere around Pd drastically. Therefore, there should not be any particular influence of Ph groups on the second coordination sphere associated with external interaction between the allyl ligand and the solvent or the counteranion. Consequently, we did not perform any ONIOM calculations on systems such as 3 and 4 with dhpe replaced by dppe.
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84962390536
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note
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31P NMR data indicate the absence of radical character in solution.
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84962404687
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The observed EXAFS scattering data were not presented in the paper or Supporting Information of ref 1.
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