A Three‐Coordinate Copper(II) Amide from Reductive Cleavage of a Nitrosamine

Abstract

A NO‐velty: A copper(I) β‐diketiminate activates the nitrosamine Ph2NNO to give a rare, three‐coordinate copper(II) amide, [(Me2NN)CuNPh2]. Reaction of this amide with NOgas returns Ph2NNO as well as a mixed‐valence species with NO‐functionalized β‐diketiminate ligands (see scheme; Cu light blue, N dark blue, O red). Thus, both the cleavage and formation of R2NNO bonds may take place at a common copper center.

The Persistent Radical Effect in Organic Synthesis

“…Thea uthors described the CuÀNb ond as at wocenter three-electron p-bond with an unpaired electron in the p*o rbital (Figure 49 b). [292] Calculations supported the suggested combination of the alkyl radical with the amine ligand, which is referred to as "radical capture"a nd can be considered as aformal homolytic substitution at nitrogen. [290] Based on this seminal work, other radical Cu-catalyzed CÀN bond formations at activated CÀHs ites with amides,s ulfonamides,i mides, [293] carbamates, [294] sulfoximines, [295] and Weinreb amides [296] as the nucleophilic Nsources have been developed.…”

Polynuclear Cu4L4 Copper(II) Aminyl Radical Coordination Complexes

“…The X-ray crystal structures and magnetic properties of 1 and 2 are described, and these experimental results are supported by density functional theory (DFT) calculations. There are very few reported examples of metal aminyl radical complexes − and, to our knowledge, none that are polynuclear.…”

Three-Coordinate Copper(II) Alkynyl Complex in C–C Bond Formation: The Sesquicentennial of the Glaser Coupling

“…The frozen glass EPR spectrum of 3 in toluene at 80 K is axially biased with g 1 = 2.178, g 2 = 2.040, and g 3 = 2.050 with A 1 (Cu) = 130, A 2 (Cu) = 290, and A 3 (Cu) = 130 MHz, respectively (Figure S6). These data are in good agreement with previously reported axially biased three-coordinate [Cu II ]–X species (X = amide, alkoxide, thiolate, and halide) with g 1 ≈ 2.20 and g 2,3 ≈ 2.05. − The IR spectrum of 3 exhibits ν CC at 2187 cm –1 (Figure S7), while the optical spectrum of 3 in toluene shows a strong band at λ max = 580 nm (4300 M –1 cm –1 ) (Figure S4).…”