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Title: Carbon–hydrogen bond activation, C–N bond coupling, and cycloaddition reactivity of a three-coordinate nickel complex featuring a terminal imido ligand

Here, the three-coordinate imidos (dtbpe)Ni=NR (dtbpe = tBu 2PCH 2CH 2PtBu 2, R = 2,6- iPr 2C 6H 3, 2,4,6-Me 3C 6H 2 (Mes), and 1-adamantyl (Ad)), which contain a legitimate Ni–N double bond as well as basic imido nitrogen based on theoretical analysis, readily deprotonate HC≡CPh to form the amide acetylide species (dtbpe)Ni{NH(Ar)}(C≡CPh). In the case of R = 2,6- iPr 2C 6H 3, reductive carbonylation results in formation of the (dtbpe)Ni(CO) 2 along with the N–C coupled product keteneimine PhCH=C=N(2,6- iPr 2C 6H 3). Given the ability of the Ni=N bond to have biradical character as suggested by theoretical analysis, H atom abstraction can also occur in (dtbpe)Ni=N{2,6- iPr 2C 6H 3} when this species is treated with HSn( nBu) 3. Likewise, the microscopic reverse reaction—conversion of the Ni(I) anilide (dtbpe)Ni{NH(2,6- iPr 2C 6H 3)} to the imido (dtbpe)Ni=N{2,6- iPr 2C 6H 3}—is promoted when using the radical Mes*O (Mes* = 2,4,6- tBu 3C 6H 2). Reactivity studies involving the imido complexes, in particular (dtbpe)Ni=N{2,6- iPr 2C 6H 3}, are also reported with small, unsaturated molecules such as diphenylketene, benzylisocyanate, benzaldehyde, and carbon dioxide, including the formation of C–N and N–N bonds by coupling reactions. In additionmore » to NMR spectroscopic data and combustion analysis, we also report structural studies for all the cycloaddition reactions involving the imido (dtbpe)Ni=N{2,6- iPr 2C 6H 3}.« less
 [1] ;  [2] ;  [3] ;  [1] ;  [4]
  1. The Univ. of Chicago, Chicago, IL (United States); Univ. of North Texas, Denton, TX (United States)
  2. The Univ. of Chicago, Chicago, IL (United States); Univ. of Vermont, Burlington, VT (United States)
  3. The Univ. of Chicago, Chicago, IL (United States); Univ. of Notre Dame, Notre Dame, IN (United States)
  4. The Univ. of Chicago, Chicago, IL (United States)
Publication Date:
Grant/Contract Number:
Published Article
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 53; Journal Issue: 24; Journal ID: ISSN 0020-1669
American Chemical Society (ACS)
Research Org:
Univ. of North Texas, Denton, TX (United States); Univ. of Chicago, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
OSTI Identifier:
Alternate Identifier(s):
OSTI ID: 1345643