1、Chapter 13 Lanthanide Complexes and Their Applications,一. Typical Lanthanide Complexes,Lanthanide Carbene,J. Am. Chem. Soc., 2007, 129 (17), 5360 -5361.,Organometallics, 2007, 26 (13), 3167 -3172,Organometallics, 2008, ASAP Article,Lanthanide Phosphinidene Complex,J. AM. CHEM. SOC. 2008, 130, 2408-2
2、409,二. Reactivity,1. Catalytic Hydrogenation,2. Lanthanide Complexes Catalyzed Hydroamination/ Cyclization Reactions,Marks, T. J. et al, Organometallics 1999, 18, 2568,Marks, T. J. ; et al, J. Am. Chem. Soc. 1999, 121, 3633.,Livinghouse, T. et al, Adv. Synth. Catal. 2006, 348, 701-704.,Lanthanide Co
3、mplexes Catalyzed Hydroamination/Cyclization Reactions of aminoalkynes,3. Lanthanide Complexes Catalyzed Hydrophosphination/Cyclization Reactions,Marks, T. J. et al, J. Am. Chem. Soc. 2000, 122, 1824. Marks, T. J. et al, Organometallics 2003, 22, 4630,4. Catalytic Hydrosilylation,Livinghouse, T. ; e
4、t al, Organometallics 2004, 23, 12-14.,5. Catalytic Hydroboration Reaction,6. Guanylation(胍化反应) of Aromatic Amines,Building Block exists in many bioactive compounds,Zhang, W.; Nishiura, M.; Hou, Z. Chem. Eur. J. 2007, 13, 4037.,Catalytic Addition of the Amine to the Carbodiimides,Catalytic Addition
5、of the Amines to the Carbodiimides,Catalytic Activity of the Cp-Free Lanthanide Amides on the Addition of Amines to Carbodiimides,Plot of Yields of Guanidine versus Reaction Time. The Reaction was performed by treating 1 equiv. of aniline with 1 equiv. of N, N-dicyclohexylcarbodiimide.,Catalytic Add
6、ition of the C-H Bond to the Carbodiimide,Catalytic Addition of the alkynes to the Carbodiimides,Zhou, S. ; Wang, S. * et al, Organometallics 2007, 26, 3755. Li, Q.; Wang, S.* et al, J. Org. Chem. 2007, 72, 6763.,7. Lanthanide Complexes Catalyzed Olefin Polymerization,Cat. = Me2Si(Me4C5)(C5H3R*)LnN(
7、SiMe3)2O(CH2H2C9H6)2LnN(SiMe3)2,Qian, C. T.; et al, Organometallics 2001, 20, 3106. Yamamoto, Y.; Marks, T. J. et al, J. Am. Chem. Soc. 1995, 117, 3276. Anwander, R.; et al, Organometallics 2003, 22, 1212.,8. Lanthanide Complexes Initiated Cannizzaro Type Disproportionation,The methodology for the p
8、reparation of amide from aldehyde,Beckmann Rearrangement,Indirect method,Catalytic reaction,Optimization of the reaction conditions,Reaction conditions: toluene as solvent; room temperature; 2-3d,The results of the reaction of aldehydes with lithium amide catalyzed by YCl3,aReaction conditions: tolu
9、ene as solvent; room temperature;bIsolated yield based on the lithium amide; cIsolated yields in the absence of YCl3 are shown in parentheses.,The effects of lanthanide metal on the reaction,The mechanism of the catalytic reaction,The results of reaction of aldehydes with yttrium amide (Me3Si)2N3Y(-
10、Cl)Li(THF)3,The results of the reaction probed by GC-MS,The process of the hydride transfer in the reaction,The proposed mechanism for the Cannizarro-type reaction,Zhang, L.; Wang, S. et al. J. Org. Chem. 2006, 71, 3149-3153.,9. Catalytic Cyclotrimerization of Aromatic Isocyanates,Shen, Q.; et al, O
11、rganometallics 2002, 21, 2529. Shen, Q.; et al, Organometallics 1997, 16, 3711.,Can Lanthanide Amides Selectively Catalyze Cyclotrimerization of Aromatic Isocyanates ?,If the lanthanide amides have different Metal-Nitrogen bonds, Whats the selectivity?,Synthesis of the lanthanide amides of Incorpora
12、ting a diamido ligand with a CH2SiMe2 link,Dy Complex,Sm complex,Yb complex,Y complex,?,Optimized conditions on the cyclotrimerization of phenyl isocyanate,Table. The influence of different rare earth metal amides on the cyclotrimerization of phenyl isocyanate,continued,Data for the Cyclotrimerizati
13、on of Different Isocyanates,Conditions, solvent: THF; a solvent: toluene,Wu, Y.; Wang, S.; et al, Inorg. Chem. 2008, in press.,Synthesis of the lanthanide amides incorporating a diamido ligang with a Me2Si Bridge,Ln = Yb(7), Y(8), Eu(9), Sm(11), Nd(11),Yb Complex,Sm complex,Nd Complex,Y Complex,Cata
14、lytic Activity of the Complexes on Cyclotrimerization of Phenyl Isocyanate,Catalyst:(Me2Si)(2,6-iPr2C6H3)N2SmN(SiMe3)2(THF) (9),Influence of different rare earth metal amides on the cyclotrimerization of phenyl isocyanate,a Catalyst loading: 0. 25 mol %; b Isolated yield by running the reaction in T
15、HF at 40 C for 12h. c catalyst loading: 1 mol %; d Isolated yield by running the reaction in THF at 60 C for 24h,Data for the cyclotrimerization of different isocyanates,Crystal Structures of cyclotrimerization products,Selective Reaction of Different Metal-Nitrogen Bonds with Grease,Ytterbium compl
16、ex,Samarium complex,Proposed Catalytic Cycle,Heterolysis of the Ln-N Bond,Can the Ln-N Bond be Homolytic Cleavage?,10. Homolysis of Lanthanide Metal-Nitrogen Bond,Synthesis and Characterization of Tetracoordinated Lanthanide Amides,N(1)-Yb-N(2) 114.83(18) N(1)-Yb-N(3) 117.88(18) N(3)-Yb-N(2) 117.2(2
17、) Cl-Yb-N(1) 100.77(13) Cl-Yb-N(2) 100.71(14) Cl-Yb-N(3) 100.59(13),Zhou, S.; Wang, S*. et al, Polyhedron 2003, 22, 1019.,Homolysis of the Yb-N Bond,Heteroatom Substituted Group Effect,(Me3Si)2N3LnIII(-Cl)Li(THF)3(Ln = Yb, Eu, Sm),Sheng, E.; Wang, S. Organometallics 2003, 22, 684.,Proposed Mechanism
18、,Wang, S.; Zhou, S.; et al Organometallics 2003, 22, 3546,Wang, S.; Tang, X.; Vega, A.; Saillard, J.-Y.; et al. Organometallics 2006, 25, 2399-2401. Organometallics, 2007, 26, 1512-1522.,Controlled Synthesis of rac-Oganometallic Compounds,Rac-Lanthanide(II) and Lanthanide(III) complexes,Rac-Divalent and trivalent lanthanide complexes,europium complex,Ytterbium complex,
