Kieber-Emmons Matthew T, Annaraj Jamespandi, Seo Mi Sook, Van Heuvelen Katherine M, Tosha Takehiko, Kitagawa Teizo, Brunold Thomas C, Nam Wonwoo, Riordan Charles G
Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, USA.
J Am Chem Soc. 2006 Nov 8;128(44):14230-1. doi: 10.1021/ja0644879.
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.
通过两条独立的合成路线制备了一种“端基”Ni2+超氧加合物，并通过光谱和计算方法确定了其结构。镍配位化学中的这种新结构类型得到了共振拉曼光谱和电子顺磁共振光谱特征的支持，前者显示出与显著超氧特征一致的高频ν（O-O）模式（1131 cm-1）。Ni2+超氧加合物以定量产率将三苯基膦氧化为三苯基氧膦。
