TY - JOUR
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.
UR - http://www.scopus.com/inward/record.url?scp=85021631766&partnerID=8YFLogxK
U2 - 10.1021/jacs.7b04158
DO - 10.1021/jacs.7b04158
M3 - Article
AN - SCOPUS:85021631766
SN - 0002-7863
VL - 139
SP - 8718
EP - 8724
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 25
ER -