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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 that2results from a nitrene by a carbene metathesis reaction in which N₂acts as a delivery vehicle and forms N₂CH₂as a side product. In the case of3, 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 for2and3, in addition to an independent synthesis for the former.

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 that2results from a nitrene by a carbene metathesis reaction in which N₂acts as a delivery vehicle and forms N₂CH₂as a side product. In the case of3, 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 for2and3, in addition to an independent synthesis for the former.