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- Title
Divergent Pathways Involving 1,3‐Dipolar Addition and N−N Bond Splitting of an Organic Azide across a Zirconium Methylidene.
- Authors
Kurogi, Takashi; Mane, Manoj V.; Zheng, Shuai; Carroll, Patrick J.; Baik, Mu‐Hyun; Mindiola, Daniel J.
- Abstract
Abstract: The zirconium methylidene (PNP)Zr=CH2(OAr) (<bold>1</bold>) reacts with N3Ad to give two products (PNP)Zr=NAd(OAr) (<bold>2</bold>) and (PNP)Zr(η2‐N=NAd)(N=CH2)(OAr) (<bold>3</bold>), both resulting from a common cycloaddition intermediate (PNP)Zr(CH2N3Ad)(OAr) (<bold>A</bold>). Using a series of control experiments in combination with DFT calculations, it was found that <bold>2</bold> 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 <bold>3</bold>, 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 <bold>2</bold> and <bold>3</bold>, in addition to an independent synthesis for the former.
- Subjects
ZIRCONIUM compounds; AZIDES; CARBENES; CHEMICAL bonds; RING formation (Chemistry)
- Publication
Angewandte Chemie, 2018, Vol 130, Issue 7, p1996
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201711587