Metal atoms collinear with the spiro carbon of 6,6-open adducts, M2@C80(Ad) (M = La and Ce, Ad = adamantylidene).
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.
Yamada
Michio
M
Center for Tsukuba Advanced Research Alliance, University of Tsukuba, Tsukuba, Ibaraki 305-8577, Japan.
Someya
Chika
C
Wakahara
Takatsugu
T
Tsuchiya
Takahiro
T
Maeda
Yutaka
Y
Akasaka
Takeshi
T
Yoza
Kenji
K
Horn
Ernst
E
Liu
Michael T H
MT
Mizorogi
Naomi
N
Nagase
Shigeru
S