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W(CO)3(Ph2PC2H4PPh2)(η(2)-Sc3N@Ih-C80/Sc3N@D5h-C80):内嵌富勒烯空气稳定单核配合物的区域选择性合成及晶体学表征

W(CO)3(Ph2PC2H4PPh2)(η(2)-Sc3N@Ih-C80/Sc3N@D5h-C80): regioselective synthesis and crystallographic characterization of air-stable mononuclear complexes of endohedral fullerenes.

作者信息

Bao Lipiao, Liu Bin, Li Xiaofang, Pan Changwang, Xie Yunpeng, Lu Xing

机构信息

State Key Laboratory of Materials Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, 1037 Luoyu Road, Wuhan, 430074 China.

出版信息

Dalton Trans. 2016 Aug 7;45(29):11606-10. doi: 10.1039/c6dt00790b. Epub 2016 Apr 14.

Abstract

The organometallic chemistry of endohedral metallofullerenes has lagged far behind that of empty fullerenes. Herein, we report a highly regioselective coordination reaction involving two Sc3N@C80 isomers and W(CO)4(Ph2PC2H4PPh2) (1), which affords only one mononuclear complex for each Sc3N@C80 isomer (2a for Sc3N@Ih-C80 and 2b for Sc3N@D5h-C80). X-ray results demonstrate that the tungsten center coordinates with the cages in an η(2) fashion on a [6,6]-bond in both cases, forming the first derivatives with a closed three membered ring for Sc3N@C80. Although IR and absorption spectroscopic results reveal relatively weak exohedral-metal to ligand π back-donation in both 2a and 2b, they show remarkable air-stability which promises their potential uses in related fields. Moreover, the coordination has narrowed down the electrochemical gaps of the parent Sc3N@C80 isomers, making the complexes better electron donors but worse electron acceptors than the corresponding precursors.

摘要

内嵌金属富勒烯的有机金属化学发展远远落后于空心富勒烯。在此,我们报道了一个涉及两种Sc3N@C80异构体与W(CO)4(Ph2PC2H4PPh2) (1)的高度区域选择性配位反应,该反应为每种Sc3N@C80异构体仅提供一种单核配合物(Sc3N@Ih-C80对应的为2a,Sc3N@D5h-C80对应的为2b)。X射线结果表明,在这两种情况下,钨中心均以η(2)方式与笼在一个[6,6]键上配位,形成了首个具有闭合三元环的Sc3N@C80衍生物。尽管红外光谱和吸收光谱结果表明2a和2b中均存在相对较弱的外表面金属到配体的π反馈配位,但它们表现出显著的空气稳定性,这预示了它们在相关领域的潜在用途。此外,配位作用缩小了母体Sc3N@C80异构体的电化学能隙,使得配合物成为比相应前体更好的电子供体但更差的电子受体。

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