Premium
Divergent Pathways Involving 1,3‐Dipolar Addition and N−N Bond Splitting of an Organic Azide across a Zirconium Methylidene
Author(s) -
Kurogi Takashi,
Mane Manoj V.,
Zheng Shuai,
Carroll Patrick J.,
Baik MuHyun,
Mindiola Daniel J.
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201711587
Subject(s) - nitrene , zirconium , chemistry , azide , cycloaddition , carbene , metathesis , salt metathesis reaction , medicinal chemistry , crystallography , stereochemistry , polymerization , organic chemistry , polymer , catalysis
The zirconium methylidene (PNP)Zr=CH 2 (OAr) ( 1 ) reacts with N 3 Ad to give two products (PNP)Zr=NAd(OAr) ( 2 ) and (PNP)Zr(η 2 ‐N=NAd)(N=CH 2 )(OAr) ( 3 ), both resulting from a common cycloaddition intermediate (PNP)Zr(CH 2 N 3 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 2 acts as a delivery vehicle and forms N 2 CH 2 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.