Catalytic nitrene transfer by a zirconium(iv) redox-active ligand complex

This communication describes the Pd(OAc)2-catalyzed intermolecular amidation reactions of unactivated sp2 and sp3 C-H bonds using primary amides and potassium persulfate. The substrates containing a pendent oxime or pyridine group were amidated with excellent chemo- and regioselectivities. It is noteworthy that reactive C-X bonds were well-tolerated and a variety of primary amides can be effective nucleophiles for the Pd-catalyzed C-H amidation reactions. For the reaction of unactivated sp3 C-H bonds, beta-amidation of 1 degrees sp3 C-H bonds versus 2 degrees C-H bonds is preferred. The catalytic reaction is initiated by chelation-assisted cyclopalladation involving C-H bond activation. Preliminary mechanistic study suggested that the persulfate oxidation of primary amides should generate reactive nitrene species, which then reacted with the cyclopalladated complex. Show more

The synthesis and structure of the beta-diketiminato Ni(I) lutidine adducts [MexNN]Ni(2,4-lutidine) (x = 2 (2); x = 3 (3)) are described which serve as synthons to the "naked" 13-electron [MexNN]Ni fragments in reactions with N3Ad to give Ni-imido complexes. The singly bridged imide {[Me2NN]Ni}2(mu-NAd) (4) possesses short Ni-Ni (2.506(1) A) and Ni-N(imido) distances (1.732(4)-1.752(4) A). Steric modification of the beta-diketiminate ligand to include an additional methyl group in the N-aryl 4-position affords the Ni(III) terminal imide [Me3NN]Ni=NAd (8) isolated in 52% yield. The X-ray structure of terminal imide 8 reveals a contracted Ni-N(imido) bond distance (1.662(2) A) and an only somewhat bent imido linkage (Ni-N-C = 164.5(2) degrees ) consistent with a significant degree of multiple bond character. Frozen glass EPR studies of 5 indicate a rhombic environment in which one of the signals exhibits strong hyperfine coupling (A = 22 G) to the imido 14N (I = 1) nucleus. The terminal imide 5 undergoes complete imido group transfer to CO and CNBut to give AdNCO and AdNCNBut, respectively, as well as with PMe3 to afford AdN=PMe3. Exemplifying the radical character at the imido N atom, 5 adds to cobaltocene and abstracts a H atom from 1,4-cyclohexadiene to give the Ni(II)-amides [Me3NN]Ni-NAd(eta4-C5H5)CoCp (7) and [Me3NN]Ni-NHAd (8). Show more