Department of Chemistry and Biochemistry, University of California, 1156 High Street, Santa Cruz, California 95064, USA.
J Am Chem Soc. 2012 Jan 25;134(3):1412-5. doi: 10.1021/ja209568v. Epub 2012 Jan 9.
Stable ruthenium nanoparticles were prepared by the self-assembly of 1-dodecyne onto the "bare" Ru colloid surface. The formation of a Ru-vinylidene (Ru═C═CH-R) interfacial bonding linkage was confirmed by the specific reactivity of the nanoparticles with imine derivatives to form a heterocyclic complex at the metal-ligand interface, as manifested in (1)H and (13)C NMR, photoluminescence, and electrochemical measurements in which a ferrocenyl imine was used as the labeling probe. Notably, the resulting nanoparticles could also undergo olefin metathesis reactions with vinyl-terminated molecules, as exemplified by the functionalization of the nanoparticles with 1-vinylpyrene. In sharp contrast, no reactvity was observed with 1-dodecynide-stabilized ruthenium nanoparticles with either imine or vinyl derivatives, indicating that these (deprotonated) nanoparticles were stabilized instead by the formation of a Ru-C≡ dπ bond at the metal-ligand interface.
通过 1-十二炔在“裸露”的 Ru 胶体表面的自组装，制备了稳定的钌纳米粒子。纳米粒子与亚胺衍生物的特异性反应证实了 Ru-vinylidene（Ru═C═CH-R）界面键合连接的形成，在金属-配体界面处形成杂环配合物，如（1）H 和（13）C NMR、光致发光和电化学测量所示，其中使用二茂铁亚胺作为标记探针。值得注意的是，所得的纳米粒子也可以与乙烯基封端分子进行烯烃复分解反应，例如通过 1-乙烯基芘对纳米粒子进行功能化。相比之下，用亚胺或乙烯基衍生物稳定的 1-十二炔稳定的钌纳米粒子没有观察到反应性，表明这些（去质子化的）纳米粒子通过在金属-配体界面形成 Ru-C≡dπ键而稳定。
