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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 = tBu2PCH2CH2PtBu2, R = 2,6-iPr2C6H3, 2,4,6-Me3C6H2 (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-iPr2C6H3, reductive carbonylation results in formation of the (dtbpe)Ni(CO)2 along with the N–C coupled product keteneimine PhCH=C=N(2,6- iPr2C6H3). 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-iPr2C6H3} 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-iPr2C6H3)} to the imido (dtbpe)Ni=N{2,6-iPr2C6H3}—is promoted when using the radical Mes*O (Mes* = 2,4,6-tBu3C6H2). Reactivity studies involving the imido complexes, in particular (dtbpe)Ni=N{2,6-iPr2C6H3}, 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 addition 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-iPr2C6H3}.
Authors:
 [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:
OSTI Identifier:
1165390
Grant/Contract Number:
FG02-03ER15387
Type:
Published Article
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 53; Journal Issue: 24; Journal ID: ISSN 0020-1669
Publisher:
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
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY