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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

Journal Article · · Inorganic Chemistry
DOI:https://doi.org/10.1021/ic5026153· OSTI ID:1165390
 [1];  [1];  [1];  [2];  [1]
  1. Department of Chemistry, The University of Chicago, Chicago, Illinois 60637, United States
  2. Department of Chemistry, The University of Chicago, Chicago, Illinois 60637, United States, Department of Chemistry, Center for Advanced Scientific Computing and Modeling (CASCaM), University of North Texas, Denton, Texas 76203, United States
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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}.

Research Organization:
Univ. of North Texas, Denton, TX (United States); Univ. of Chicago, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
FG02-03ER15387
OSTI ID:
1165390
Alternate ID(s):
OSTI ID: 1345643
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Vol. 53 Journal Issue: 24; ISSN 0020-1669
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 47 works
Citation information provided by
Web of Science

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Figures / Tables (14)

Scheme 1(p. 2)figure Scheme 1
Scheme 2(p. 5)figure Scheme 2
Scheme 3(p. 5)figure Scheme 3
Figure 1(p. 6)figure Figure 1
Figure 2(p. 6)figure Figure 2
Figure 3(p. 7)figure Figure 3
Scheme 4(p. 7)figure Scheme 4
Figure 4(p. 8)figure Figure 4
Table 1(p. 8)table Table 1
Scheme 5(p. 9)figure Scheme 5
Table 2(p. 9)table Table 2
Figure 5(p. 10)figure Figure 5
Figure 6(p. 10)figure Figure 6
Scheme 6(p. 10)figure Scheme 6

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