一种由镍（I）配合物与氧气衍生而来的单体镍-双氧加合物。
A monomeric nickel-dioxygen adduct derived from a nickel(I) complex and O2.
作者信息
Fujita Koyu, Schenker Ralph, Gu Weiwei, Brunold Thomas C, Cramer Stephen P, Riordan Charles G
机构信息
Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716, USA.
出版信息
Inorg Chem. 2004 May 31;43(11):3324-6. doi: 10.1021/ic049876n.
The nickel(I) complex [PhTt(Ad)]Ni(CO) (PhTt(Ad), phenyltris((1-adamantylthio)methyl)borate) reacts with O(2) generating a 1:1 species identified as a side-on dioxygen adduct based on its spectroscopic properties as supported by DFT computational results and by its reactivity. The Ni EXAFS data are fit to a S(3)O(2) coordination environment with short Ni-O distances, 1.85 A. The brown complex displays a rhombic EPR signal with g values of 2.24, 2.19, 2.01. DFT and INDO/S-CI computations replicate the EXAFS and EPR features and suggest that 2 is a side-on NiO(2) complex with geometric and electronic properties that are best rationalized in terms of a highly covalent Ni(II)-superoxo description. [PhTt(Ad)]Ni(O(2)) oxidizes PPh(3) to OPPh(3), NO to NO(3)(-), and [PhTt(tBu)]Ni(CO) to the nonsymmetric [PhTt(Ad)]Ni(micro-O)(2)Ni[PhTt(tBu)] dimer.
镍（I）配合物[PhTt(Ad)]Ni(CO)（PhTt(Ad)，苯基三（（1-金刚烷基硫基）甲基）硼酸酯）与O₂反应生成一种1:1的物种，根据其光谱性质、DFT计算结果及其反应活性，该物种被确定为侧基双氧加合物。镍的扩展X射线吸收精细结构（EXAFS）数据拟合为具有短Ni-O距离（1.85 Å）的S(3)O(2)配位环境。棕色配合物显示出菱形电子顺磁共振（EPR）信号，g值为2.24、2.19、2.01。DFT和INDO/S-CI计算重现了EXAFS和EPR特征，并表明2是一种侧基NiO₂配合物，其几何和电子性质根据高度共价的Ni(II)-超氧描述最能得到合理说明。[PhTt(Ad)]Ni(O₂)将三苯基膦（PPh₃）氧化为三苯基氧膦（OPPh₃），将一氧化氮（NO）氧化为硝酸根离子（NO₃⁻），并将[PhTt(tBu)]Ni(CO)氧化为不对称的[PhTt(Ad)]Ni(μ-O)₂Ni[PhTt(tBu)]二聚体。
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