Effects of the counteranion on the pyrazole-nitrile coupling reaction mediated by nickel(II) ions

Chang Chih Hsieh, Chia Jung Lee, Yih Chern Horng

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

The reaction of Ni(ClO4)2 with 4 equiv of pyrazole (pzH) in MeCN leads to [Ni(pzH)2(HN= C(Me)pz)2](ClO4) 2 via the intermediate [Ni(MeCN)2(pzH)4] (ClO4)2, which is the first pyrazole-nitrile coupling reaction activated by a Ni(II) complex. The reaction is also successfully conducted with other nitries RCN bearing an electron-donating group (R = Et, Bz) and is counteranion-specific. The reaction proceeds more quickly with NO 3̄ as counteranion than with ClO4̄, and BF4̄ is found to be unsatisfactory for the coupling reaction. As for the X-ray crystal structures, [Ni(MeCN) 2(pzH)4](ClO4)2 possesses stronger pyrazolyl NH... anion hydrogen-bonding interactions than does [Ni(MeCN) 2(pzH)4](BF4)2. The same trend is also observed by solution IR (pyrazolyl NH) analysis. The supramolecular structure of the complex [Ni(pzH)2(HN=C(Me)pz)2](ClO 4)2 displays a two-dimensional network dominated by cooperative face-toface π-π stacking and edge-to-face CH...π bonding interactions. In addition, a mechanism based on anion-mediated/hydrogen-bonding- driven proton transfer for the coupling reaction is proposed.

Original languageEnglish
Pages (from-to)4923-4928
Number of pages6
JournalOrganometallics
Volume28
Issue number17
DOIs
Publication statusPublished - 2009 Sep 14

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Nitriles
nitriles
Nickel
nickel
Ions
ions
Anions
Hydrogen bonds
Bearings (structural)
Proton transfer
anions
hydrogen
Crystal structure
Display devices
perchlorate
pyrazole
X rays
interactions
methylidyne
Electrons

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

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abstract = "The reaction of Ni(ClO4)2 with 4 equiv of pyrazole (pzH) in MeCN leads to [Ni(pzH)2(HN= C(Me)pz)2](ClO4) 2 via the intermediate [Ni(MeCN)2(pzH)4] (ClO4)2, which is the first pyrazole-nitrile coupling reaction activated by a Ni(II) complex. The reaction is also successfully conducted with other nitries RCN bearing an electron-donating group (R = Et, Bz) and is counteranion-specific. The reaction proceeds more quickly with NO 3̄ as counteranion than with ClO4̄, and BF4̄ is found to be unsatisfactory for the coupling reaction. As for the X-ray crystal structures, [Ni(MeCN) 2(pzH)4](ClO4)2 possesses stronger pyrazolyl NH... anion hydrogen-bonding interactions than does [Ni(MeCN) 2(pzH)4](BF4)2. The same trend is also observed by solution IR (pyrazolyl NH) analysis. The supramolecular structure of the complex [Ni(pzH)2(HN=C(Me)pz)2](ClO 4)2 displays a two-dimensional network dominated by cooperative face-toface π-π stacking and edge-to-face CH...π bonding interactions. In addition, a mechanism based on anion-mediated/hydrogen-bonding- driven proton transfer for the coupling reaction is proposed.",
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Effects of the counteranion on the pyrazole-nitrile coupling reaction mediated by nickel(II) ions. / Hsieh, Chang Chih; Lee, Chia Jung; Horng, Yih Chern.

In: Organometallics, Vol. 28, No. 17, 14.09.2009, p. 4923-4928.

Research output: Contribution to journalArticle

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AB - The reaction of Ni(ClO4)2 with 4 equiv of pyrazole (pzH) in MeCN leads to [Ni(pzH)2(HN= C(Me)pz)2](ClO4) 2 via the intermediate [Ni(MeCN)2(pzH)4] (ClO4)2, which is the first pyrazole-nitrile coupling reaction activated by a Ni(II) complex. The reaction is also successfully conducted with other nitries RCN bearing an electron-donating group (R = Et, Bz) and is counteranion-specific. The reaction proceeds more quickly with NO 3̄ as counteranion than with ClO4̄, and BF4̄ is found to be unsatisfactory for the coupling reaction. As for the X-ray crystal structures, [Ni(MeCN) 2(pzH)4](ClO4)2 possesses stronger pyrazolyl NH... anion hydrogen-bonding interactions than does [Ni(MeCN) 2(pzH)4](BF4)2. The same trend is also observed by solution IR (pyrazolyl NH) analysis. The supramolecular structure of the complex [Ni(pzH)2(HN=C(Me)pz)2](ClO 4)2 displays a two-dimensional network dominated by cooperative face-toface π-π stacking and edge-to-face CH...π bonding interactions. In addition, a mechanism based on anion-mediated/hydrogen-bonding- driven proton transfer for the coupling reaction is proposed.

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