The zirconium methylidene (PNP)Zr=CH₂(OAr) (1) reacts with N₃Ad to give two products (PNP)Zr=NAd(OAr) (2) and (PNP)Zr(η²‐N=NAd)(N=CH₂)(OAr) (3), both resulting from a common cycloaddition intermediate (PNP)Zr(CH₂N₃Ad)(OAr) (A). Using a series of control experiments in combination with DFT calculations, it was found that 2 results from a nitrene by a carbene metathesis reaction in which N₂ acts as a delivery vehicle and forms N₂CH₂ as a side product. In the case of 3, N−N bond splitting of the azide at the α‐position allowed the isolation of a rare example of a parent ketimide complex of zirconium. Isotopic labeling studies and solid‐state X‐ray analysis are presented for 2 and 3, in addition to an independent synthesis for the former.

中文翻译：

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涉及亚甲基锆上有机叠氮化物的1,3-偶极加成和N-N键分裂的发散途径

锆亚甲基（PNP）的Zr = CH ₂（桨）（1）与N-起反应₃的广告得到两种产物（PNP）的Zr = NAD（OAR）（2）和（PNP）的Zr（η ² -N = NAD） （N ＝ CH ₂）（OAr）（3），两者均由共同的环加成中间体（PNP）Zr（CH ₂ N ₃ Ad）（OAr）（A）产生。使用一系列对照实验并结合DFT计算，发现2是由碳烯通过卡宾复分解反应得到的，其中N ₂用作传递载体并形成N ₂ CH ₂作为副产物。在3的情况下，叠氮化物在α位的NN键断裂使得可以分离出一个罕见的锆母体酮亚胺化物配合物实例。同位素标记研究和固态X射线分析针对2和3进行了介绍，此外还针对前者进行了独立的合成。