金属氮化物团簇富勒烯的新型三氟甲基化衍生物：Sc₃N@I(h)-C₈₀ (CF₃)₁₄和Sc₃N@D(5h)-C₈₀ (CF₃)₁₆

New trifluoromethylated derivatives of metal nitride clusterfullerenes: Sc₃N@I(h)-C₈₀ (CF₃)₁₄ and Sc₃N@D(5h)-C₈₀ (CF₃)₁₆.

作者信息

Wei Tao, Tamm Nadezhda B, Yang Shangfeng, Troyanov Sergey I

机构信息

Hefei National Laboratory for Physical Sciences at Microscale, CAS Key Laboratory of Materials for Energy Conversion & Department of Materials Science and Engineering, University of Science and Technology of China (USTC), Hefei 230026 (China), Fax: (+86) 551-3601750.

出版信息

Chem Asian J. 2014 Sep;9(9):2449-52. doi: 10.1002/asia.201402573. Epub 2014 Jul 8.

DOI:10.1002/asia.201402573

PMID:25044462

Abstract

Trifluoromethylated derivatives of Sc3N@I(h)-C80 and Sc3N@D(5h)-C80 were synthesized by the reaction with CF3I at 440 °C. HPLC separation of the mixture of Sc3N@D(5h)-C80(CF3)n derivatives resulted in isolation and X-ray structure determination of Sc3N@D(5h)-C80(CF3)16, which represents a precursor of the known Sc3N@D(5h)-C80(CF3)18. Among the CF3 derivatives of Sc3N@I(h)-C80, two new isomers of Sc3N@I(h)-C80(CF3)14 (Sc-14-VI and Sc-14-VII) were isolated by HPLC, and their molecular structures were determined by X-ray diffraction, thus enabling a comprehensive comparison of altogether seven isomers. Two types of addition patterns with different orientations of the Sc3N cluster relative to the I(h)-C80 fullerene cage were established. In particular, Sc-14-VII represents a direct precursor of the known Sc3N@I(h)-C80(CF3)16-II. All molecular structures exhibit an ordered position of a Sc3N cluster inside the fullerene C80 cage.

摘要

通过在440°C下与CF3I反应合成了Sc3N@I(h)-C80和Sc3N@D(5h)-C80的三氟甲基化衍生物。对Sc3N@D(5h)-C80(CF3)n衍生物混合物进行HPLC分离，得到了Sc3N@D(5h)-C80(CF3)16的分离物并进行了X射线结构测定，它是已知的Sc3N@D(5h)-C80(CF3)18的前体。在Sc3N@I(h)-C80的CF3衍生物中，通过HPLC分离出了两种新的Sc3N@I(h)-C80(CF3)14异构体（Sc-14-VI和Sc-14-VII），并通过X射线衍射确定了它们的分子结构，从而能够对总共七种异构体进行全面比较。建立了两种Sc3N簇相对于I(h)-C80富勒烯笼具有不同取向的加成模式。特别是，Sc-14-VII是已知的Sc3N@I(h)-C80(CF3)16-II的直接前体。所有分子结构都显示出Sc3N簇在富勒烯C80笼内的有序位置。