Reactivity of Organolanthanide and Organolithium Complexes Containing the Guanidinate Ligands toward Isocyanate or Carbodiimide: Synthesis and Crystal Structures
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- 作者：Jie Zhang ; Xigeng Zhou ; Ruifang Cai ; and Linhong Weng
- 刊名：Inorganic Chemistry
- 出版年：2005
- 出版时间：February 7, 2005
- 年：2005
- 卷：44
- 期：3
- 页码：716 - 722
- 全文大小：153K
- 年卷期：v.44,no.3(February 7, 2005)
- ISSN：1520-510X
文摘
The direct reactions of (C5H5)2LnCl with LiN=C(NMe2)2 proceeded at room temperature in THF under pure nitrogento yield the lanthanocene guanidinate complexes [(C5H5)2Ln(
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1:2-N=C(NMe2)2)]2 (Ln = Gd (1), Er (2)). Treatmentof phenyl isocyanate with complexes 1 and 2 results in monoinsertion of phenyl isocyanate into the Ln-N(-Gua)bond to yield the corresponding insertion products [(C5H5)2Ln(-1:2-OC(N=C(NMe2)2)NPh)]2 (Ln = Gd (3), Er(4)), presenting the first example of unsaturated organic small molecule insertion into the metal-guanidinate ligandbond. Further investigations indicate that N,N'-diisopropylcarbodiimide does not react with complexes 1 and 2under the same conditions; however, it readily inserts into the lithium-guanidinate ligand bond of LiN=C(NMe2)2.As a synthon of the insertion product Li[(iPrN)2C(N=C(NMe2)2)], its reaction with (C5H5)2LnCl gives the novelorganolanthanide complexes containing the guanidinoacetamidinate ligand, (C5H5)2Ln[(iPrN)2C(N=C(NMe2)2)] (Ln= Yb (5), Er (6), Dy (7)). All complexes were characterized by elemental analysis and spectroscopic properties.The structures of complexes 1, 3, 5 and 7 were determined through X-ray single-crystal diffraction analysis.
-1:2-N=C(NMe2)2)]2 (Ln = Gd (1), Er (2)). Treatmentof phenyl isocyanate with complexes 1 and 2 results in monoinsertion of phenyl isocyanate into the Ln-N(-Gua)bond to yield the corresponding insertion products [(C5H5)2Ln(-1:2-OC(N=C(NMe2)2)NPh)]2 (Ln = Gd (3), Er(4)), presenting the first example of unsaturated organic small molecule insertion into the metal-guanidinate ligandbond. Further investigations indicate that N,N'-diisopropylcarbodiimide does not react with complexes 1 and 2under the same conditions; however, it readily inserts into the lithium-guanidinate ligand bond of LiN=C(NMe2)2.As a synthon of the insertion product Li[(iPrN)2C(N=C(NMe2)2)], its reaction with (C5H5)2LnCl gives the novelorganolanthanide complexes containing the guanidinoacetamidinate ligand, (C5H5)2Ln[(iPrN)2C(N=C(NMe2)2)] (Ln= Yb (5), Er (6), Dy (7)). All complexes were characterized by elemental analysis and spectroscopic properties.The structures of complexes 1, 3, 5 and 7 were determined through X-ray single-crystal diffraction analysis.