Application Of Bridged Guanidinate And Bis (β-diketiminato) Lanthanide(Ⅱ) Complexes In C-P Bond Formation

In this thesis a series of lanthanide（II） complexes based on the three carbon/naphthalene linker guanidinate were synthesized. Furthermore, catalysis of these complexes for the hydrophosphination of alkenes/alkynes and diphenylphosphane were researched. Besides, catalytic behavior of a series of bis（β-diketiminato） lanthanide（II） complexes for the hydrophosphonylation of aldehydes and unactivated ketones were studied. The main results were as follows.1. Reaction of anhydrous EuCl₃ with L¹Li₂（THF）（L¹Li₂ = [i Pr（Me3Si）NC（Ni Pr）N（CH₂）₃NC（Ni Pr）N（Si Me₃）i Pr]Li₂）, followed by reduction reaction with sodium/potassium alloy in suit, giving a three carbon bridged divalent europium complex（L¹Eu）2（1）. Reaction of anhydrous Yb Cl3（1.5 equiv）with L¹Li₂（THF） followed by reduction reaction with sodium/potassium alloy in suit, or firstly reaction of anhydrous Yb Cl3 with L¹Li₂（THF） was carried out, producing L1 Yb Cl, then to which 0.5 equiv Yb Cl3 was added. Meanwhile, sodium/potassium alloy was put into that aboving solution, which both could give a three carbon bridged divalent ytterbium complex（Yb L1）2（3）。2. Reaction of 1,8-diaminonaphthalene with n-Bu Li（in hexane） in 1:2 molar ratio, then two equivalent of N,N-diisopropyl carbodiimide. Then the responding solution was added to anhydrous Eu Cl3, followed by reduction reaction with sodium/potassium alloy in suit, getting a naphthalene linker divalent europium complex [Eu（L2H2）（THF）]2（2）.3. The catalytic activity of bridged guanidinate lanthanide（II） complexes 1-2 for the hydrophosphination of styrene and diphenylphosphane were studied. We screened in a systematic way the reaction conditions such as solvent, the loading of catalyst, temperature, catalyst, time etc. The results displayed that complexes 1-2 both could catalyzed this reaction. Among them complex 1 exhibited higher activity. Under the condition of 60 oC, 1 mol% and free solvent, complex 1 showed good substrate scope.4. Based on the above result, the hydrophosphination of phenylacetylene and diphenylphosphane with complexes 1-2 were explored. Comple 1 was found to enjoy excellent catalytic behavior, but the scope of alkynes substrates was quite limited.5. The hydrophosphonylation of benzaldehyde was explored with a series of bis（β-diketiminato） lanthanide（II） complexes: Eu（L2,6-ipr₂）2·CH3C6H5（4）,（L2,6-ipr2 = [N（2,6-iPr2C6H3）C（Me）]2CH-）; Eu（L2,6-Me₂）₂（THF）（5）,（L2,6-Me2 = [N（2,6-Me₂C₆H₃）C（Me）]2CH-）; Eu（L2,4,6-Me3）2（THF）（6）,（L2,4,6-Me3 = [N（2,4,6-Me3C6H2）C（Me）]2CH-）; Eu（L2,6-ipr2Ph）2（7）,（L2,6-ipr2 Ph = [（2,6-iPr2C6H3）NC（Me）CHC（Me）N（C6H5）]–）; Sm（L2,6-ipr2）2·CH3C6H5（8）; Yb（L2,6-ipr2Ph）2（9）; Yb（L2-Me）2（THF）（10）,（L2-Me = [N（2-Me C6H4）C（Me）]2CH–）. Complexes 4-10 were all able to make the reaction carry out efficiently. Considering, when choosing the condition of complex 10, 25 oC, 0.08 mol% and free solvent, we could get a quite high yield（ over 90%）, no matter the aromatic aldehyde included electron-withdrawing, electron-donating or other heteroatoms.6. By exploring further, we found complexes 5, 6, 8, 9 could active the hydrophosphonylation of acetophenone, receiving α-hydroxy phosphonates in moderate yield. Generally, we explored the reaction substrate in the presence of complex 10, 25 oC 0.5 mol% and the substrate of ketones had a good range.