Formation of the Palladium(IV) Complex [(Me3tacn)PdIVMe3]+ through Aerobic Oxidation of (Me3tacn)PdIIMe2 (Me3tac

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• 作者：Julia R. Khusnutdinova ; Fengrui Qu ; Ying Zhang ; Nigam P. Rath ; Liviu M. Mirica
• 刊名：Organometallics
• 出版年：2012
• 出版时间：July 9, 2012
• 年：2012
• 卷：31
• 期：13
• 页码：4627-4630
• 全文大小：234K
• 年卷期：v.31,no.13(July 9, 2012)
• ISSN：1520-6041

文摘

The dimethyl Pd^II complex (Me₃tacn)Pd^IIMe₂ (Me₃tacn = N,N鈥?N鈥?trimethyl-1,4,7-triazacyclononane) undergoes facile aerobic oxidation to yield the stable species [(Me₃tacn)Pd^IVMe₃]⁺. EPR, UV鈥搗is, and ESI-MS studies suggest an inner-sphere mechanism for the oxidation of (Me₃tacn)PdMe₂ by O₂ and formation of Pd^IV species. In addition, the structurally characterized complex [(Me₃tacn)Pd^IVMe₃]I undergoes selective elimination of ethane at elevated temperatures. Overall, this system represents one of the first examples of aerobic oxidation of a Pd^II organometallic precursor to yield a well-defined Pd^IV product, supporting the role of Pd^IV species as viable intermediates in Pd-mediated catalytic or stoichiometric aerobic oxidative transformations.