CUHK electronic theses & dissertations collection

Chapter 1 presents an overview of the lanthanide chemistry with cyclopentadienyl and cyclopentadienyl-free ligands. The chemistry of divalent lanthanide is also briefly reviewed.Chapter 2 describes the preparation and characterization of a series of lanthanide(III) amides derived from the bidentate 2-pyridyl amido ligand [N(SiMe3)(2-C5H3 N-6-Me)] (L 1): [Ln(L1)3] [L1=, Ln = Yb (7), Sm (8), Dy (9)], [Ln(L 1)3(THF)] [Ln = Pr (10), Gd (11)], and [(L1)2Ln(mu-OBut) 2Li(THF)x] (x = 2, Ln = Nd (12), Sm ( 13), Eu (14); x = 1, Ln = Dy (15), Er ( 16)).Chapter 3 describes the preparation and characterization of divalent lanthanide amides derived from L1 and the more bulky [N(SiButMe2)(2-C5H 3 N-6-Me)] (L2) ligands, namely [Ln(Ln) 2(tmeda)] (n = 1, Ln = Yb (17), Eu (20); n = 2, Ln = Yb (18)), [(L1)3YbK(THF)] (19), and [(L2)3EuK(tmeda)] ( 21). Complexes 17-21 were prepared by direction reaction of LnI2(THF)), (Ln = Eu or Yb) with the potassium salts of L 1 and L2. Attempts to synthesize the analogous Sm(II) and Dy(II) derivatives were unsuccessful. The divalent samarocene, [(C 5H3(SiMe3)2)2Sm(THF)] ( 24), was also prepared in our work. Subsequent reaction of 24 with 1,3-dicyclocarbodiimide (DCC) in THF yielded the dinuclear Sm(III) bisamidinate compound [(Cp")2Sm(NC6H11) 2CC(H11C6N)2Sm(Cp")2] ( 25).Chapter 4 describes the preparation and characterization of divalent Sm, Eu and Yb complexes derived from the bulky dianionic [R 2Si(NC6H3Pri2-2,6) 2]2- (R = Me or Ph) ligands. Treatment of LnI2(THF)), (Ln = Sm, Eu, and Yb) with K2(Ln)(THF) x (L3 = Me2Si(NC6H3Pr i2-2,6)2, L4 = Ph2Si(NC 6H3Pri2-2,6)2) afforded the corresponding Ln(II) derivatives, [(L4)2Sm{K(OEt 2)}2] (36), [(C)2Ln {K(THF) 2}2] (n = 4, Ln = Yb (39); n = 3, Ln = Sm ( 37), Yb (40), Eu (44), and the mononuclear compound [(L4)Yb(THF)3] (38).However, attempts to prepare divalent Nd and Dy complexes of the dianionic ligands were unsuccessful. Only the corresponding Nd(III) and Dy(III) complexes were isolated. In our studies, five lanthanide(III) complexes, namely [{K(THF) 6}Ln(L4)2] (Ln = Sm (34), Yb (41), Nd (42), Dy (43)) and [(L 3)2SmK(THF)3] (35) were isolated.This thesis describes the synthetic and structural studies of lanthanide complexes derived from the monoanionic 2-pyridyl amido ligands [N(R)(2-C 5H3N-6-Me)]- (R = SiMe3, SiBu tMe2), the dianionic [R2Si(NC 6H3 Pri2-2,O2] 2- (R = Me or Ph) ligands, and the bis(trimethylsilyl)-cyclopentadienyl [C5H3(SiMe3)2]- ligand.Pan, Chengling."February 2008."Source: Dissertation Abstracts International, Volume: 70-03, Section: B, page: 1665.Thesis (Ph.D.)--Chinese University of Hong Kong, 2008.Includes bibliographical references.Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web.Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web.Abstracts in English and Chinese.School code: 1307