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Synthesis and Characterization of Bridged Bis(Phenolate) Lanthanide(Ⅱ) Complexes and Their Reaction Activity

Author: DuZhu
Tutor: ShenZuo
School: Suzhou University
Course: Organic Chemistry
Keywords: Bridging aryloxy Rare earth metals Synthesis Structure Catalytic
CLC: O627.3
Type: PhD thesis
Year: 2011
Downloads: 69
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The paper-bridged aryloxy ligand synthesized a series of bridging aryloxy divalent rare earth complexes, and the effects of these divalent rare earth complexes with carbide diimine aza-butadiene oxidation reduction reactions. Also inspected the divalent rare earth complexes catalyzed carbodiimide amine guanidine reaction carbodiimide the terminal alkyne amidination reaction catalytic activity. The main findings are as follows: 1 [ONNO] 1 H 2 ([ONNO] = the C 4 H 8 N 2 [1,4 - (2-O-3 ,5-di-tBu-C 6 H 2 CH 2 ) 2 ]) and [ONNO] 2 H 2 ([ONNO] 2 = C 4 H 8 N 2 [1,4 - (2-O-3-tBu-5-Me-C 6 H 2 CH 2 ) 2 ]) and Ln [N (SiMe3) 2 ] the 2 (THF) 2 molar ratio of 1:1 reaction has been three divalent rare earth complexes [the ONNO] 12Yb2 1 [ONNO] 2 Yb (THF) 3 2, [ONNO] 2 2 Eu2 (THF) 24. [ONNO] 2 H 2 Yb [N (SiMe3) 2 ] 2 (TMEDA) 1 : 1 molar ratio of the the complexes [ONNO] for Yb2 7 of 2 2 . All complexes have been X-ray single crystal diffraction, infrared spectroscopy, elemental analysis. 1,2 and 7, the 1H NMR was measured. 2 ScS complexes and complexes 7 and the carbodiimide oxidation reduction reaction. Complex 2 in THF solvent with carbodiimide reaction of the hydroxy-bridged complex [ONNO] YB2 (OH) 2 2 2 4, toluene as the solvent is still generated complexes, complexes 7 and the carbodiimide reaction in toluene solvent generates bridge carbene complexes [(ONNO) . Yb] (iPr-NCN-iPr) · C 7 H 8 5 [(ONNO) 2 Yb] (Cy-NCN-Cy) · C7H8 3, carbodiimide participate in the reaction as a two-electron oxidant in the reaction. We first discovered piperazine alkyl-bridged aryloxy ytterbium (II) complex matter with the carbodiimide reaction when the THF ring-opening reaction to generate hydroxyl bridged rare earth complexes. 3 investigated the reactivity of the bridge carbene complexes. Complex 3 with PhNCO by the molar ratio of 1:6 The reaction complexes [(ONNO) 2 Yb] 2 (PhNCO) 2 (PHN) and organic matter C 29 H 29 N 5 O 4 · 10, the complex with PhNCO by the [(ONNO) 4 Yb] 2 (PhNCO) 2 (1: 6 molar ratio of the reaction was carried out by a complex in PHN) · 9 and organics C 29 H 29 N 5 O 4 · 10 This result indicates that the bridge carbene complexes of rare earth nitrogen bond can be inserted into the carbene carbon and due to PhNCO insert freed to generate organic 10 further and PhNCO reaction, we propose a mechanism of the reaction. We also investigated complexes 3 and the reaction of CO 2 CO2 into the toluene solution of the complex 3, the complexes (ONNO) 2 YbO 2 C (iPr) N = C [(iPr) HN] 2 C = N (iPr) O 2 CYb (ONNO) 2 (THF) 2 12. As the CO2 insertion leads to further conversion, which has not yet been reported in the literature. 4 ONNO] 3 H 2 ([ONNO] 3 H 2 to = C 3 < / sub> H 6 N 2 [1,4 - (2-O-3 ,5-di-tBu-C 6 H < sub> 2 the CH 2 ) 2 ]) and Yb [N (SiMe 3 ) 2 ] 2 (THF) 2 1:1 molar ratio of the complex [ONNO] 3 Yb (DME) (THF) 13 complexes 13 and carbodiimide reaction in THF solution has been complex [ONNO of 3 2Yb 2 (MeO) 2 14 . [ONNO] 3 H 2 and Yb [N (SiMe 3 ) 2 ] 2 < / sub> (THF) 2 after the 1:1 molar ratio of the reaction in situ generated divalent ytterbium complexes in solution, THF, was added isopropyl carbodiimide reaction was carried out to obtain complexes [ONNO] 3 Yb [μ-(iPr) NCHN (iPr)] 15. Also use [ONNO] 3H2 Yb [N (SiMe 3 ) 2 ] 2 (TMEDA) in toluene solvent reaction situ Yb complexes, isopropyl carbodiimide reaction was carried out by a complex {[ONNO] 3Yb} 2 [mu-(IPR) NCN (IPR)] 16. It can be seen that the presence of a solvent effect imidazolidinyl bridged bis-aryl group and a divalent ytterbium complex was carbodiimide reaction. We generate complexes 14 and 15 of the radical reaction mechanism. 5 Synthesis of the first example to determine the structure of the hetero atom-bridged bis-aryl group of divalent samarium complexes, and studied its reactivity. [ONNO] 2 H 2 and Sm [N (SiMe 3 ) 2 ] 2 < / sub> (THF) 2 at 1:1 molar ratio, the end of the reaction after adding two equivalents of HMPA quad-core ring complexes [ONNO] 2 4Sm4 (HMPA) 8 17. Complexes generated in situ generated 17 and isopropyl carbodiimide reaction complexes (ONNO) 2 Sm {(NiPr) 2 CC (NiPr) 2 } Sm (ONNO) 2 18, isopropyl carbodiimide participate in the reaction as a single-electron oxidant; complex 17 is generated in situ and cyclohexyl carbodiimide reaction generated complexes [(ONNO) . 2 Sm] 2 (Cy-NCN-Cy) 19, cyclohexyl carbodiimide as two-electron oxidants involved in the reaction. First discovered carbodiimide reaction generates two reaction mode product with a divalent rare earth complexes. 6 divalent rare earth complexes catalyzed amine with carbodiimide imine guanidine reaction system. Discovered by the screening of catalyst Sm [N (SiMe 3 ) 2 ] 2 (THF) 2 in the absence of solvent under the conditions of the highest activity, regardless of electron withdrawing aromatic amines or for electrons of the aromatic amine with a carbodiimide reaction to generate the corresponding guanidine are excellent yield. Generally relatively poor activity of fatty amines, under the conditions at 80 ° C. The generated with excellent yield the corresponding guanidine. Our success isolated intermediates of the reaction, the reaction reasonable reaction mechanism. 7 of the divalent rare earth complexes catalyzed terminal alkyne carbodiimide amidine reaction. Compound IV shows a high catalytic activity for the terminal alkyne and an addition reaction of the carbodiimide. Activity trends in terms of ligand-I lt;-MeC5H4 lt;-Aro lt;-N (TMS) 2 Yb lt; central metal; Eu LT; Sm. Sm [N (SiMe 3 ) 2 ] 2 (THF) 2 in THF solvent catalyst screening revealed under the conditions of the highest activity, regardless of the end of the electron-withdrawing alkynyl or for electronic terminal alkyne with the carbodiimide reaction to generate relatively good yield of the corresponding amidine. We have successfully isolated from the reaction intermediate product, and proposed reaction mechanism of the reaction. 8 the first to study the reaction of the non-cyclopentadienyl-bridged aryloxy divalent rare earth complexes with aza-butadiene. (ONNO) 12 Yb 2 (ONO) of 5 Yb (THF) 3 IPR 2 C 6 H 3 N = CHCH = NC 6 H 3 i Pr 2 reaction complexes (ONNO) 12 Yb 2 (iPr 2 C < sub> 6 H 3 NCH = CHNC 6 H 3 i Pr 2 < / sub>) 20 and complexes (ONO) 52Yb2 (the iPr 2 C 6 H 3 NCH = CHNC 6 H 3 i Pr 2 ) 21, In order to investigate the spatial effect and charge effect of aza-butadiene, we will be back (ONNO) 2 Yb (THF) 3 with IPR of 2 C 6 H 3 N = C (Me) C (Me) = NC 6 H 3 i Pr 2 reaction complexes ( ONNO) 2 Yb (ONNO) 2 Yb (iPr 2 C 6 H 3 NC (Me) = C (Me) NC 6 H 3 i Pr 2 ) 22. Aza-butadiene due to the structural changes in the mode of reaction to changes, but aza-butadiene are involved in the reaction as electric double-oxidant itself generate the dianion ligand. In order to examine the central metal on the reaction, we studied the reaction of divalent samarium and divalent europium aza-butadiene, respectively complexes (ONNO) 2 Sm III (iPr 2 C 6 H 3 NCHCHNC 6 H 3 i the Pr 2 - ·) 23 (ONNO) , of EuIII (iPr 2 the C 6 < / sub> H 3 NCHCHNC 6 H 3 i Pr 2 - ·) 25. Aza-butadiene in the reaction as a single-electron oxidant participate in the reaction itself generates free radicals monoanionic ligand. It is worth mentioning are complexes exist stably in THF, 20, 21, 22, 23, 25 and the THF decomposition, 25 the presence of a solvent effect, related to the nature of this result illustrates the stability of the complex with a central metal.

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CLC: > Mathematical sciences and chemical > Chemistry > Organic Chemistry > Elements in organic compounds > The first III group elements, organic compounds
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