Transient Formation and Reactivity of a High-Valent Nickel(IV) Oxido Complex

Sandeep K. Padamati; Davide Angelone; Apparao Draksharapu; Gloria Primi; David J. Martin; Moniek Tromp; Marcel Swart; Wesley R. Browne

doi:10.1021/jacs.7b04158

Transient Formation and Reactivity of a High-Valent Nickel(IV) Oxido Complex

Sandeep K. Padamati, Davide Angelone, Apparao Draksharapu, Gloria Primi, David J. Martin, Moniek Tromp, Marcel Swart^*, Wesley R. Browne

^*Corresponding author for this work

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Abstract

A reactive high-valent dinuclear nickel(IV) oxido bridged complex is reported that can be formed at room temperature by reaction of [(L)₂Ni(II)₂(μ-X)₃]X (X = Cl or Br) with NaOCl in methanol or acetonitrile (where L = 1,4,7-trimethyl-1,4,7-triazacyclononane). The unusual Ni(IV) oxido species is stabilized within a dinuclear tris-μ-oxido-bridged structure as [(L)₂Ni(IV)₂(μ-O)₃]²⁺. Its structure and its reactivity with organic substrates are demonstrated through a combination of UV-vis absorption, resonance Raman, ¹H NMR, EPR, and X-ray absorption (near-edge) spectroscopy, ESI mass spectrometry, and DFT methods. The identification of a Ni(IV)-O species opens opportunities to control the reactivity of NaOCl for selective oxidations.

Original language	English
Pages (from-to)	8718-8724
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	139
Issue number	25
DOIs	https://doi.org/10.1021/jacs.7b04158
Publication status	Published - 28-Jun-2017

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title = "Transient Formation and Reactivity of a High-Valent Nickel(IV) Oxido Complex",

abstract = "A reactive high-valent dinuclear nickel(IV) oxido bridged complex is reported that can be formed at room temperature by reaction of [(L)2Ni(II)2(μ-X)3]X (X = Cl or Br) with NaOCl in methanol or acetonitrile (where L = 1,4,7-trimethyl-1,4,7-triazacyclononane). The unusual Ni(IV) oxido species is stabilized within a dinuclear tris-μ-oxido-bridged structure as [(L)2Ni(IV)2(μ-O)3]2+. Its structure and its reactivity with organic substrates are demonstrated through a combination of UV-vis absorption, resonance Raman, 1H NMR, EPR, and X-ray absorption (near-edge) spectroscopy, ESI mass spectrometry, and DFT methods. The identification of a Ni(IV)-O species opens opportunities to control the reactivity of NaOCl for selective oxidations.",

author = "Padamati, {Sandeep K.} and Davide Angelone and Apparao Draksharapu and Gloria Primi and Martin, {David J.} and Moniek Tromp and Marcel Swart and Browne, {Wesley R.}",

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T1 - Transient Formation and Reactivity of a High-Valent Nickel(IV) Oxido Complex

AU - Padamati, Sandeep K.

AU - Angelone, Davide

AU - Draksharapu, Apparao

AU - Primi, Gloria

AU - Martin, David J.

AU - Tromp, Moniek

AU - Swart, Marcel

AU - Browne, Wesley R.

PY - 2017/6/28

Y1 - 2017/6/28

N2 - A reactive high-valent dinuclear nickel(IV) oxido bridged complex is reported that can be formed at room temperature by reaction of [(L)2Ni(II)2(μ-X)3]X (X = Cl or Br) with NaOCl in methanol or acetonitrile (where L = 1,4,7-trimethyl-1,4,7-triazacyclononane). The unusual Ni(IV) oxido species is stabilized within a dinuclear tris-μ-oxido-bridged structure as [(L)2Ni(IV)2(μ-O)3]2+. Its structure and its reactivity with organic substrates are demonstrated through a combination of UV-vis absorption, resonance Raman, 1H NMR, EPR, and X-ray absorption (near-edge) spectroscopy, ESI mass spectrometry, and DFT methods. The identification of a Ni(IV)-O species opens opportunities to control the reactivity of NaOCl for selective oxidations.

AB - A reactive high-valent dinuclear nickel(IV) oxido bridged complex is reported that can be formed at room temperature by reaction of [(L)2Ni(II)2(μ-X)3]X (X = Cl or Br) with NaOCl in methanol or acetonitrile (where L = 1,4,7-trimethyl-1,4,7-triazacyclononane). The unusual Ni(IV) oxido species is stabilized within a dinuclear tris-μ-oxido-bridged structure as [(L)2Ni(IV)2(μ-O)3]2+. Its structure and its reactivity with organic substrates are demonstrated through a combination of UV-vis absorption, resonance Raman, 1H NMR, EPR, and X-ray absorption (near-edge) spectroscopy, ESI mass spectrometry, and DFT methods. The identification of a Ni(IV)-O species opens opportunities to control the reactivity of NaOCl for selective oxidations.

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EP - 8724

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 25

ER -

Transient Formation and Reactivity of a High-Valent Nickel(IV) Oxido Complex

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