An Unusual Cobalt Azide Adduct That Produces a Nitrene Species for Carbon–Hydrogen Insertion Chemistry

• DOI: 10.1021/acs.inorgchem.6b01114
• Publication Date: 2016-07-25T13:25:30Z
• Authors: Lauren N. Grant; Maria E. Carroll; Patrick J. Carroll; Daniel J. Mindiola
• Keywords: Nitrene; Carbon fibers

A family of Co(II) complexes supported by the bulky, dianionic bis(pyrrolyl)pyridine pincer ligand pyrr2py [pyrr2py2– = 3,5-tBu2-bis(pyrrolyl)pyridine] are reported in this work. These compounds include 1-OEt2, 1·toluene, and 1-N3Ad (Ad 1-adamantyl), latter which is prepared via addition N3Ad to 1-OEt2 [1 (pyrr2py)Co]. While four-coordinate systems having a ion confined cis-divacant octahedral geometry, complex 1·toluene possesses T-shaped environment where toluene interstitial intercalated between two (pyrr2py)Co molecules. Complex notable that organic azide binds metal through γ-N κ1 fashion. Photolysis results N2 extrusion formation C–H insertion product [(pyrrpypyrrNHAd)Co] (2). We propose 2 form nitrene (NAd) into one tBu bond, thus resulting pendant secondary amine. Complexes have been structurally characterized, case we also present electrochemical data.