Metal atoms collinear with the spiro carbon of 6,6-open adducts, M2@C80(Ad) (M = La and Ce, Ad = adamantylidene).
Metal atoms collinear with the spiro carbon of 6,6-open adducts, M2@C80(Ad) (M = La and Ce, Ad = adamantylidene).
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DOI：
10.1021/ja073924w
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发表时间：
2008-01
影响因子：
15
通讯作者：
M. Yamada;Chika I. Someya;T. Wakahara;T. Tsuchiya;Y. Maeda;T. Akasaka;K. Yoza;E. Horn;Michael T. H. Liu
中科院分区：
文献类型：
--
作者：
M. Yamada;Chika I. Someya;T. Wakahara;T. Tsuchiya;Y. Maeda;T. Akasaka;K. Yoza;E. Horn;Michael T. H. Liu
M2@C80 （M = La和Ce）与2-金刚烷-2,3′-[3H]-重氮嘧啶(1)的光化学反应通过加成碳得到相应的加合物。通过光谱和单晶x射线结构分析对加合物进行了表征。加合物La2@C80(Ad) （2, Ad = adamantylidene）的晶体学数据表明，两个La原子与6,6开加合物的螺旋碳共线。值得注意的是，由于碳的加入，La-La距离被大大延长了。对加合物Ce2@C80(Ad)(3)的顺磁13C NMR谱分析表明，在室温溶液中，两个Ce原子也与螺旋碳共线。通过密度泛函计算确定了独特的金属位置。
The photochemical reaction of M2@C80 (M = La and Ce) with 2-adamantane-2,3'-[3H]-diazirine (1) affords the corresponding adducts by carbene addition. The adducts were characterized by spectroscopic and single-crystal X-ray structure analyses. Crystallographic data for the adduct La2@C80(Ad) (2, Ad = adamantylidene) reveal that the two La atoms are collinear with the spiro carbon of the 6,6-open adduct. It is noteworthy that the La-La distance is highly elongated by the addition of carbene. Paramagnetic 13C NMR spectral analysis of the adduct Ce2@C80(Ad) (3) indicates that the two Ce atoms are also collinear with the spiro carbon at room temperature in solution. The unique metal positions were confirmed by density functional calculations.