通过钯-钯键的断裂将双核钯(III)和单核钯(IV)化学连接起来。
Connecting binuclear Pd(III) and mononuclear Pd(IV) chemistry by Pd-Pd bond cleavage.
机构信息
Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138, USA.
出版信息
J Am Chem Soc. 2012 Jul 25;134(29):12002-9. doi: 10.1021/ja304401u. Epub 2012 Jul 17.
Oxidation of binuclear Pd(II) complexes with PhICl(2) or PhI(OAc)(2) has previously been shown to afford binuclear Pd(III) complexes featuring a Pd-Pd bond. In contrast, oxidation of binuclear Pd(II) complexes with electrophilic trifluoromethylating ("CF(3)(+)") reagents has been reported to afford mononuclear Pd(IV) complexes. Herein, we report experimental and computational studies of the oxidation of a binuclear Pd(II) complex with "CF(3)(+)" reagents. These studies suggest that a mononuclear Pd(IV) complex is generated by an oxidation-fragmentation sequence proceeding via fragmentation of an initially formed, formally binuclear Pd(III), intermediate. The observation that binuclear Pd(III) and mononuclear Pd(IV) complexes are accessible in the same reactions offers an opportunity for understanding the role of nuclearity in both oxidation and subsequent C-X bond-forming reactions.
先前的研究表明，二核 Pd(II) 配合物与 PhICl₂ 或 PhI(OAc)₂ 反应会生成具有 Pd-Pd 键的二核 Pd(III) 配合物。相比之下，用亲电的三氟甲基化（“CF₃⁺”）试剂氧化二核 Pd(II) 配合物已被报道会生成单核 Pd(IV) 配合物。在此，我们报告了用“CF₃⁺”试剂氧化双核 Pd(II) 配合物的实验和计算研究。这些研究表明，单核 Pd(IV) 配合物是通过氧化-断裂序列生成的，该序列通过最初形成的、形式上的双核 Pd(III) 中间体的断裂进行。在相同的反应中可以得到双核 Pd(III) 和单核 Pd(IV) 配合物这一观察结果为理解核数在氧化和随后的 C-X 键形成反应中的作用提供了机会。
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