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Calix[4]arene-plumbylene complexes Pb[Calixt-Bu(O)2(OR)2], where R=benzyl, 9-fluorenyl, SitBuMe2, and SiiPr3, have been synthesized by the reaction of Lappert's plumbylene Pb[N(SiMe3)2]2 with the corresponding 1,3-diethers of calix[4]arene. The products have been fully characterized by 1H, 13C{1H}, and 207Pb NMR spectroscopy, elemental analysis, and X-ray diffraction analysis. The products adopt two different forms depending on the R groups: the alkyl derivatives were obtained as exo-isomers in which the lead atom resides outside the cavity of the calix[4]arene, while the silyl derivatives were isolated as endo-isomers where the lead atom is situated inside the cavity. X-ray diffraction studies revealed that the lead(II) atoms in the exo- and endo-isomers are coordinated by the ethereal oxygen atoms (OR) and the aromatic rings (ArOR), respectively, which are maintained in solution as evidenced by 207Pb NMR studies.  相似文献   
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Energy differences, ΔXS‐t (X = E, H and G) (ΔXS‐t = X(singlet)‐X(triplet)) between singlet (s) and triplet (t) states are calculated at B3LYP/6‐311++G (3df,2p). The DFT calculations show that the triplet state of C4H4C is a ground state with planar conformer respect to its corresponding nonplanar singlet state. Both singlet and triplet states of C4H4M (M = Si, Ge, Sn and Pb) have a planar conformer with the singlet ground state. Four isodesmic reactions are presented for determining the stability energies, SE. NICS calculations are carried out for C4H4M to determine the aromatic character.  相似文献   
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