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Synthesis And Characterization Of Organo Rare Earth Metal Alkyl Complexes Supported By Amidinate Ligands And Their Catalytic Behavior For Polymerization

Posted on:2009-04-10Degree:MasterType:Thesis
Country:ChinaCandidate:X L WangFull Text:PDF
GTID:2121360245960246Subject:Organic Chemistry
Abstract/Summary:PDF Full Text Request
A series of mono(amidinate) rare earth metal bis(alkyl) complexes were prepared by alkyl elimination reaction between amidine and rare earth metal tris(alkyl) complexes Ln(CH2SiMe3)3(THF)2. The neutral amidinate rare earth metal alkyl complexes were tested to polymerize L-lactide.1. Reaction of amidine [PhC(N-2,6-Me2C6H3)2]H with Y(CH2SiMe3)3(THF)2 in 1:1 molar ratio, after workup, afforded the mono(amidinate) yttrium bis(alkyl) complex [PhC(N-2,6-Me2C6H3)2]Y(CH2SiMe3)2(THF)2 (1). Complex 1 was characterized by elemental analysis, IR spectroscopy, and 1H NMR spectroscopy.2. Treatments of [CyC(N-2,6-iPr2C6H3)2]H with one equiv. of Ln(CH2SiMe3)3(THF)2 (Ln = Y, Lu) gave the mono(amidinate) rare earth bis(alkyl) complexes [CyC(N-2,6-iPr2C6H3)2]Ln(CH2SiMe3)2(THF) [Ln = Y (2), Lu (3)]. Reaction of Nd(CH2SiMe3)3(THF)2, which was formed in situ from the reaction of NdCl3 with three equiv. of LiCH2SiMe3 in THF at room temperature, with one equiv. of [CyC(N-2,6-iPr2C6H3)2]H afforded the"ate"complexes [CyC(N-2,6-iPr2C6H3)2]Nd(CH2SiMe3)2(μ-Cl)Li(THF)3 (4). Complexes 2 and 3 were characterized by elemental analysis, IR spectroscopy, 1H NMR spectroscopy and 13C NMR spectroscopy. Complexes 3 and 4 were characterized by X-ray diffraction, and revealed that the geometry of central metals is pseudo-pyramid.3. Reactions of [CyC(N-2,6-Me2C6H3)2]H with one equiv. of Ln(CH2SiMe3)3(THF)2 (Ln = Y, Lu, Nd) gave the mono(amidinate) rare earth metal bis(alkyl) complexes [CyC(N-2,6-Me2C6H3)2]Ln(CH2SiMe3)2(THF)2 [Ln = Y (5), Lu (6), Nd (7)]. Complexes 5 and 6 were characterized by elemental analysis, IR spectroscopy, 1H NMR spectroscopy and 13C NMR spectroscopy. Complex 7 was characterized by IR spectroscopy. The structures of complexes 5 and 7 were confirmed by X-ray diffraction.4. Treatments of H[(N-2,6-iPr2C6H3)2C]C6H4[C(N-2,6-iPr2C6H3)2]H with two equiv. of tris(alkyl) rare earth metal complexes Ln(CH2SiMe3)3(THF)2 (Ln = Y, Lu) at room temperature, after workup, afforded the bridged-amidinate-ligated rare earth metal tetra(alkyl) complexes[(THF)(Me3SiCH2)2Ln[(N-2,6-iPr2C6H3)2C]C6H4[C(N-2,6-iPr2C6H3)2]Ln(CH2SiMe3)2(THF)n] [Ln = Y, (8), n = 2; Lu (9), n = 1]. Complexes 8 and 9 were characterized by elemental analysis, IR spectroscopy, 1H NMR spectroscopy and 13C NMR spectroscopy.5. Reactions of H[(N-2,6-Me2C6H3)2C]C6H4[C(N-2,6-Me2C6H3)2]H with two equiv. of Ln(CH2SiMe3)3(THF)2 (Ln = Y, Lu) at room temperature gave [(THF)(Me3SiCH2)2Ln[(N-2,6-Me2C6H3)2C]C6H4[C(N-2,6-Me2C6H3)2]Ln(CH2SiMe3)2(THF)] [Ln = Y (10), Lu (11)]. Complexes 10 and 11 were characterized by elmental analysis, IR spectroscopy, 1H NMR spectroscopy and 13C NMR spectrocopy.6. Treatment of H[(N-2,6-R2C6H3)2C]Cy[C(N-2,6-R2C6H3)2]H (R = iPr, Me) with two equiv. of (YCH2SiMe3)3(THF)2 at room temperature afforded [(THF)(Me3SiCH2)2Y[(N-2,6-R2C6H3)2C]Cy[C(N-2,6-R2C6H3)2]Y(CH2SiMe3)2(THF)n] [R = iPr (12), n = 1; R = Me (13), n = 2]. Complexes 12 and 13 were characterized by elemental analysis, IR spectroscopy, 1H NMR spectroscopy and 13C NMR spectroscopy.7. These neutral amidinate-ligated rare earth metal alkyl complexes are active for the polymerization of L-lactide.
Keywords/Search Tags:amidinate, organo rare earth metal alkyl complexes, synthesis, characterization, polymerization
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