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Formation of the Palladium(IV) Complex [(Me3tacn)PdIVMe3]+ through Aerobic Oxidation of (Me3tacn)PdIIMe2 (Me3tacn = N,N′,N″-Trimethyl-1,4,7-triazacyclononane)

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Figshare2016-02-20 更新2026-04-29 收录
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https://figshare.com/articles/dataset/Formation_of_the_Palladium_IV_Complex_Me_sub_3_sub_tacn_Pd_sup_IV_sup_Me_sub_3_sub_sup_sup_through_Aerobic_Oxidation_of_Me_sub_3_sub_tacn_Pd_sup_II_sup_Me_sub_2_sub_Me_sub_3_sub_tacn_i_N_i_i_N_i_i_N_i_Trimethyl_1_4_7_triazacyclononane_/2506978
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The dimethyl PdII complex (Me3tacn)­PdIIMe2 (Me3tacn = N,N′,N″-trimethyl-1,4,7-triazacyclononane) undergoes facile aerobic oxidation to yield the stable species [(Me3tacn)­PdIVMe3]+. EPR, UV–vis, and ESI-MS studies suggest an inner-sphere mechanism for the oxidation of (Me3tacn)­PdMe2 by O2 and formation of PdIV species. In addition, the structurally characterized complex [(Me3tacn)­PdIVMe3]I undergoes selective elimination of ethane at elevated temperatures. Overall, this system represents one of the first examples of aerobic oxidation of a PdII organometallic precursor to yield a well-defined PdIV product, supporting the role of PdIV species as viable intermediates in Pd-mediated catalytic or stoichiometric aerobic oxidative transformations.
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2016-02-20
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