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

Chang Chih Hsieh; Chia Jung Lee; Yih Chern Horng

doi:10.1021/om9004753

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

Chang Chih Hsieh, Chia Jung Lee, Yih Chern Horng

Department of Chemistry

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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 ₃^̄ as counteranion than with ClO₄̄, and BF₄^̄ 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 language	English
Pages (from-to)	4923-4928
Number of pages	6
Journal	Organometallics
Volume	28
Issue number	17
DOIs	https://doi.org/10.1021/om9004753
Publication status	Published - 2009 Sep 14

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All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

Cite this

Hsieh, C. C., Lee, C. J., & Horng, Y. C. (2009). Effects of the counteranion on the pyrazole-nitrile coupling reaction mediated by nickel(II) ions. Organometallics, 28(17), 4923-4928. https://doi.org/10.1021/om9004753

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

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 {\=3} as counteranion than with ClO{\=4}, and BF{\=4} 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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AU - Hsieh, Chang Chih

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N2 - 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.

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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10.1021/om9004753