Institution: | Changchun Institute of Applied Chemistry, Academia Sinica, Changchun 130022, Jilin, People's Republic of China |
Abstract: | LnCl3 (Ln=Nd, Gd) reacts with C5H9C5H4Na (or K2C8H8) in THF (C5H9C5H4 = cyclopentylcyclopentadienyl) in the ratio of 1 : to give (C5H9C5H4)LnCl2(THF)n (orC8H8)LnCl2(THF)n], which further reacts with K2C8H8 (or C5H9C5H4Na) in THF to form the litle complexes. If Ln=Nd the complex (C8H8)Nd(C5H9C5H4)(THF)2 (a) was obtained: when Ln=Gd the 1 : 1 complex (C8H8)Gd(C%H9)(THF)](C8H8)Gd(C5H9H4)(THF)2] (b) was obtained in crystalline form. The crystal structure analysis shows that in (C8H8)Ln(C5H9C5H4)(THF)2 (Ln=Nd or Gd), the Cyclopentylcyclopentadieny (η5), cyclooctatetraenyl (η8) and two oxygen atoms from THF are coordinated to Nd3+ (or Gd3+) with coordination number 10. The centroid of the cyclopentadienyl ring (Cp′) in C5H9C5H4 group, cyclooctatetraenyl centroid (COTL) and two oxygens (THF) form a twisted tetrahedron around Nd3+ (or Gd3+). In (C8H8)Gd(C5H9C5H4)(THF), the cyclopentyl-cyclopentadienyl (η5), cyclooctatetraenyl (η8) and one oxygen atom are coordinated to Gd3+ with the coordination number of 9 and Cp′, COT and oxygen atom form a triangular plane around Gd3+, which is almost in the plane (dev. -0.0144 Å). |