Identification of an "end-on" nickel-superoxo adduct, [Ni(tmc)(O2)]+.
An "end-on" Ni2+-superoxo adduct has been prepared via two independent synthetic routes and its structure ascertained by spectroscopic and computational methods. The new structure type in nickel coordination chemistry is supported by resonance Raman and EPR spectroscopic features, the former displaying a high frequency nu (O-O) mode (1131 cm-1) consistent with significant superoxo character. The Ni2+-superoxo adduct oxidizes PPh3 to OPPh3 in quantitative yield.
Kieber-Emmons
Matthew T
MT
Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, USA.
Annaraj
Jamespandi
J
Seo
Mi Sook
MS
Van Heuvelen
Katherine M
KM
Tosha
Takehiko
T
Kitagawa
Teizo
T
Brunold
Thomas C
TC
Nam
Wonwoo
W
Riordan
Charles G
CG
D006571:Heterocyclic Compounds / Q000737:chemistry*; D015394:Molecular Structure; D009532:Nickel / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*; D013059:Spectrum Analysis, Raman; D013481:Superoxides / Q000737:chemistry*
D006571:Heterocyclic Compounds; D009942:Organometallic Compounds; D013481:Superoxides; D009532:Nickel; D010100:Oxygen