Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, PA, 19104, USA.
Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS), Daejeon, 34141, Republic of Korea.
Angew Chem Int Ed Engl. 2018 Feb 12;57(7):1978-1981. doi: 10.1002/anie.201711587. Epub 2018 Jan 16.
The zirconium methylidene (PNP)Zr=CH (OAr) (1) reacts with N Ad to give two products (PNP)Zr=NAd(OAr) (2) and (PNP)Zr(η -N=NAd)(N=CH )(OAr) (3), both resulting from a common cycloaddition intermediate (PNP)Zr(CH N Ad)(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 N acts as a delivery vehicle and forms N CH 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.
锆亚甲基（PNP）Zr=CH（OAr）（1）与 NAd 反应生成两种产物（PNP）Zr=NAd（OAr）（2）和（PNP）Zr（η-N=NAd）（N=CH）（OAr）（3），两者均来自一个共同的环加成中间体（PNP）Zr（CHNAd）（OAr）（A）。通过一系列控制实验结合 DFT 计算，发现 2 是由氮烯通过卡宾复分解反应生成的，其中 N 充当载体，并形成 NCH 作为副产物。在 3 的情况下，叠氮化物在α-位的 N-N 键的分裂允许分离出锆的罕见的母体酰亚胺络合物的实例。除了前者的独立合成外，还进行了 2 和 3 的同位素标记研究和固态 X 射线分析。
