C–N bond metathesis is a straightforward and step-economical approach for C–N bond construction. Typically, the oxidation state of the transition metal remains unchanged during C–N bond metathesis. In this report, we present computational evidence that supports a mechanism in which a new type of reversible reductive elimination/oxidative addition mode is involved in the C–N bond metathesis reaction. This reversible reductive elimination/oxidative addition-induced C–N bond metathesis pathway was found to be lower in energy compared with transimination from a Huang-complex, which is important for understanding the mechanism of Pd-catalyzed C–N bond formation reactions. Non-covalent interaction analysis was conducted to elucidate the details of the diene 1,4-migratory insertion step process and to investigate the origin of stereoselectivity for this type of reaction. We anticipate that this novel C–N bond metathesis mode may extend to other cross-coupling processes and may provide a theoretical guide for further experimental investigations.

中文翻译：

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C–N 键复分解：对使用胺类物种的钯催化闭环的机理洞察

C-N 键复分解是一种直接且步骤经济的 C-N 键构建方法。通常，过渡金属的氧化态在 C-N 键复分解过程中保持不变。在这份报告中，我们提供了支持一种机制的计算证据，在该机制中，一种新型的可逆还原消除/氧化加成模式参与了 C-N 键复分解反应。这种可逆还原消除/氧化加成诱导的 C-N 键复分解途径被发现与黄配合物的转移亚胺化相比能量较低，这对于理解 Pd 催化的 C-N 键形成反应的机制很重要。进行非共价相互作用分析以阐明二烯 1 的细节，4-迁移插入步骤过程并研究此类反应的立体选择性来源。我们预计这种新颖的 C-N 键复分解模式可能会扩展到其他交叉偶联过程，并可能为进一步的实验研究提供理论指导。