Cobalt Diazo‐Compounds: From Nitrilimide to Isocyanoamide via a Diazomethanediide Fleeting Intermediate. (8th April 2021)

• Record Type: Journal Article
• Authors: Aghazada, Sadig; Fehn, Dominik; Heinemann, Frank W.; Munz, Dominik; Meyer, Karsten
• Is Part Of: Angewandte Chemie. Volume 133:Number 20(2021)
• Page Start: 11238
• Page End: 11242
• Publication Date: 2021-04-08
• Subjects: bond activation -- cobalt -- density functional theory -- diazo compounds -- nitrilimines; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202016539
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Lithium trimethylsilyldiazomethanide and a cobalt (II) precursor with an N‐anchored tris ‐NHC (TIMEN mes ) ligand provide access to the cobalt nitrilimide 1 . Complex 1 was structurally characterized by single‐crystal X‐ray diffractometry (SC‐XRD) and its electronic structure was examined in detail, including EPR spectroscopy, SQUID magnetometry and computational analyses. The desilylation of the C ‐(trimethylsilyl)nitrilimide reveals a transient complex with an elusive diazomethanediide ligand, which substitutes one of the mesitylene rings of the ancillary ligand through C−N bond cleavage. This transformation results in the cyclometalated cobalt(II) complex 2, featuring a rare isocyanoamido‐κ‐C ligand. Abstract : Trimethylsilylium abstraction from a cobalt nitrilimide complex generates a transient cobalt diazomethanediide complex, which forms a terminal isocyanoamido ligand through a radical de‐arylation.