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Synthesis, Characterization, and Reactivity of PCN Pincer Nickel Complexes

Mousa, Abdelrazek H. LU ; Bendix, Jesper and Wendt, Ola F. LU (2018) In Organometallics 37(15). p.2581-2593
Abstract

New diamagnetic nickel(II) complexes based on an unsymmetrical (1-(3-((ditert-butylphosphino)methyl)phenyl)-N,N-dimethyl-methanamine) (PCN) pincer ligand were synthesized and characterized by 1H, 31P{1H}, and 13C{1H} NMR spectroscopy. Their molecular structures were confirmed by X-ray diffraction. Oxidation to high-valent paramagnetic Ni(III) dihalide complexes was achieved through straightforward reaction of the corresponding diamagnetic halide complexes with anhydrous CuX2 (X = Cl, Br). In agreement with this, the complexes are active in Kharasch addition of CCl4 to olefins. The reaction of the hydroxo complex (8) and the amido complex (11) with... (More)

New diamagnetic nickel(II) complexes based on an unsymmetrical (1-(3-((ditert-butylphosphino)methyl)phenyl)-N,N-dimethyl-methanamine) (PCN) pincer ligand were synthesized and characterized by 1H, 31P{1H}, and 13C{1H} NMR spectroscopy. Their molecular structures were confirmed by X-ray diffraction. Oxidation to high-valent paramagnetic Ni(III) dihalide complexes was achieved through straightforward reaction of the corresponding diamagnetic halide complexes with anhydrous CuX2 (X = Cl, Br). In agreement with this, the complexes are active in Kharasch addition of CCl4 to olefins. The reaction of the hydroxo complex (8) and the amido complex (11) with CO2 produced the hydrogen carbonate and carbamate complexes, respectively. The hydrogen carbonate complex was converted to the dinuclear nickel carbonate complex (10). The methyl (13), phenyl (14), and p-tolylacetylide (15) complexes are also described in the current study providing the first example of the hydrocarbyl nickel complexes based on an unsymmetric aromatic pincer ligand. Furthermore, the reactivity of the methyl complex toward different electrophiles has been investigated, showing that C-C bond formation is possible with aryl halides, whereas the reaction with CO2 is sluggish.

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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Organometallics
volume
37
issue
15
pages
13 pages
publisher
The American Chemical Society (ACS)
external identifiers
  • scopus:85051437942
ISSN
0276-7333
DOI
10.1021/acs.organomet.8b00333
language
English
LU publication?
yes
id
30923fd0-0f2a-4b2d-a800-9f70b9c8dd9a
date added to LUP
2018-09-10 10:54:05
date last changed
2020-01-22 07:12:34
@article{30923fd0-0f2a-4b2d-a800-9f70b9c8dd9a,
  abstract     = {<p>New diamagnetic nickel(II) complexes based on an unsymmetrical (1-(3-((ditert-butylphosphino)methyl)phenyl)-N,N-dimethyl-methanamine) (PCN) pincer ligand were synthesized and characterized by <sup>1</sup>H, <sup>31</sup>P{<sup>1</sup>H}, and <sup>13</sup>C{<sup>1</sup>H} NMR spectroscopy. Their molecular structures were confirmed by X-ray diffraction. Oxidation to high-valent paramagnetic Ni(III) dihalide complexes was achieved through straightforward reaction of the corresponding diamagnetic halide complexes with anhydrous CuX<sub>2</sub> (X = Cl, Br). In agreement with this, the complexes are active in Kharasch addition of CCl<sub>4</sub> to olefins. The reaction of the hydroxo complex (8) and the amido complex (11) with CO<sub>2</sub> produced the hydrogen carbonate and carbamate complexes, respectively. The hydrogen carbonate complex was converted to the dinuclear nickel carbonate complex (10). The methyl (13), phenyl (14), and p-tolylacetylide (15) complexes are also described in the current study providing the first example of the hydrocarbyl nickel complexes based on an unsymmetric aromatic pincer ligand. Furthermore, the reactivity of the methyl complex toward different electrophiles has been investigated, showing that C-C bond formation is possible with aryl halides, whereas the reaction with CO<sub>2</sub> is sluggish.</p>},
  author       = {Mousa, Abdelrazek H. and Bendix, Jesper and Wendt, Ola F.},
  issn         = {0276-7333},
  language     = {eng},
  month        = {08},
  number       = {15},
  pages        = {2581--2593},
  publisher    = {The American Chemical Society (ACS)},
  series       = {Organometallics},
  title        = {Synthesis, Characterization, and Reactivity of PCN Pincer Nickel Complexes},
  url          = {http://dx.doi.org/10.1021/acs.organomet.8b00333},
  doi          = {10.1021/acs.organomet.8b00333},
  volume       = {37},
  year         = {2018},
}