Nitrene-functionalized ruthenium nanoparticles
Nitrene-functionalized ruthenium nanoparticles
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DOI：
10.1039/c2jm33783e
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发表时间：
2012-08
影响因子：
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通讯作者：
Xiongwu Kang;Yang Song;Shaowei Chen
中科院分区：
文献类型：
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作者：
Xiongwu Kang;Yang Song;Shaowei Chen
以仲丁基苯为溶剂，用4-十二烷基苯磺酰叠氮和裸钌胶体（粒径为2.12 ± 0.72 nm）共沉淀法制备了由钌-氮烯π键保护的钌纳米粒子。所得纳米颗粒的热重分析（TGA）表明，在纳米颗粒表面上平均存在约84.1个配体。XPS研究表明氮和硫之间的原子比为1：1，这与叠氮化物前体热分解形成氮烯碎片一致。此外，Ru 3d和N1s电子的结合能表明RuN界面键的共价性质，这在FTIR测量中出现在1246 cm−1处的振动带。由于这样的共轭键合相互作用，广泛的粒子内电荷离域发生，和纳米粒子结合氮烯部分表现类似的偶氮衍生物，表现在紫外-可见和荧光测量。RuN界面键的形成的进一步证据突出了在独特的反应性的纳米粒子与烯烃的亚氨基转移，这是证明在光谱和电化学研究。
Ruthenium nanoparticles protected by ruthenium–nitrene π bonds were prepared by refluxing “bare” ruthenium colloids (2.12 ± 0.72 nm in diameter) and 4-dodecylbenezenesulfonyl azide in sec-butylbenzene. Thermogravimetric analysis (TGA) of the resulting nanoparticles showed that on average there were about 84.1 ligands on the nanoparticle surface. XPS studies showed a 1:1 atomic ratio between nitrogen and sulfur, consistent with the formation of nitrene fragments by the thermal decomposition of the azide precursors. In addition, the binding energies of Ru3d and N1s electrons suggested a covalent nature of the RuN interfacial linkage which appeared in FTIR measurements with a vibrational band at 1246 cm−1. Because of such conjugated bonding interactions, extensive intraparticle charge delocalization occurred, and the nanoparticle-bound nitrene moieties behaved analogously to azo derivatives, as manifested in UV-vis and fluorescence measurements. Further testimony of the formation of RuN interfacial linkages was highlighted in the unique reactivity of the nanoparticles with alkenes by imido transfer, which was evidenced in spectroscopic and electrochemical studies.