Study of the Square Planar Methylpalladium (II) Complexes Bearing Unsymmetrical α-Aminoaldimine Bidentate Ligands of Hetero Functionalities: Synthesis, Geometrical Isomerism and Reactivity

碩士 === 國立臺灣大學 === 化學研究所 === 97 === A series of unsymmetrical bidentate ligands of α-aminoaldimines in the form of R1R2NCMe2CH=NR (R1, R2 = Me, Et, c-C4H8 or R1 = iPr, tBu, R2 = H; R = Me, Et, iPr, tBu) have been synthesized using condensation of 2,2-aminoethylpropanal with such ligands can replace C...

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Main Authors: Yu-Heng Wang, 王育��
Other Authors: Jwu-Ting Chen
Format: Others
Language:zh-TW
Online Access:http://ndltd.ncl.edu.tw/handle/69756346158793745913
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spelling ndltd-TW-097NTU050650442016-05-04T04:31:48Z http://ndltd.ncl.edu.tw/handle/69756346158793745913 Study of the Square Planar Methylpalladium (II) Complexes Bearing Unsymmetrical α-Aminoaldimine Bidentate Ligands of Hetero Functionalities: Synthesis, Geometrical Isomerism and Reactivity 含胺-亞胺異官能雙牙配位基平面四邊形鈀(II)金屬錯合物之合成、幾何異構化及反應活性的研究 Yu-Heng Wang 王育�� 碩士 國立臺灣大學 化學研究所 97 A series of unsymmetrical bidentate ligands of α-aminoaldimines in the form of R1R2NCMe2CH=NR (R1, R2 = Me, Et, c-C4H8 or R1 = iPr, tBu, R2 = H; R = Me, Et, iPr, tBu) have been synthesized using condensation of 2,2-aminoethylpropanal with such ligands can replace COD in (COD)PdMeCl to give neutral methylchloropalladium complexes contain geometrical isomers with square planar configuration, and cis-trans isomerism was observed in solutions. However, it is interested that crystallographic analysis gives only single form crystal. Which geometrical isomers could be available depending on the relative stability in solution. The equilibrium constant of the isomerization may be fine-tuned in terms of the variation of the ligand substituents. Kinetic and mechanistic studies for the substitution and isomerization reactions are investigated by varied temperature 1H NMR. The rate constant of isomerization is 6.97 × 10-5 s-1 at -10℃, 5.29 × 10-4 s-1 at 0℃, and 3.49 × 10-3 s-1 at 10℃, and the activation energy is 120 kJ/mol. The geometrical isomerization is proposed to proceed via an imine dissociation and re-coordination. The CO- and CNR- inserted products of [R1R2NCMe2CH=NR]PdMeCl also contain geometrical isomers, and the reactivity is differentiated toward DMAD. Here we report the variation in insertion rate constant and proposed mechanism between cis and trans form. Jwu-Ting Chen 陳竹亭 學位論文 ; thesis 250 zh-TW
collection NDLTD
language zh-TW
format Others
sources NDLTD
description 碩士 === 國立臺灣大學 === 化學研究所 === 97 === A series of unsymmetrical bidentate ligands of α-aminoaldimines in the form of R1R2NCMe2CH=NR (R1, R2 = Me, Et, c-C4H8 or R1 = iPr, tBu, R2 = H; R = Me, Et, iPr, tBu) have been synthesized using condensation of 2,2-aminoethylpropanal with such ligands can replace COD in (COD)PdMeCl to give neutral methylchloropalladium complexes contain geometrical isomers with square planar configuration, and cis-trans isomerism was observed in solutions. However, it is interested that crystallographic analysis gives only single form crystal. Which geometrical isomers could be available depending on the relative stability in solution. The equilibrium constant of the isomerization may be fine-tuned in terms of the variation of the ligand substituents. Kinetic and mechanistic studies for the substitution and isomerization reactions are investigated by varied temperature 1H NMR. The rate constant of isomerization is 6.97 × 10-5 s-1 at -10℃, 5.29 × 10-4 s-1 at 0℃, and 3.49 × 10-3 s-1 at 10℃, and the activation energy is 120 kJ/mol. The geometrical isomerization is proposed to proceed via an imine dissociation and re-coordination. The CO- and CNR- inserted products of [R1R2NCMe2CH=NR]PdMeCl also contain geometrical isomers, and the reactivity is differentiated toward DMAD. Here we report the variation in insertion rate constant and proposed mechanism between cis and trans form.
author2 Jwu-Ting Chen
author_facet Jwu-Ting Chen
Yu-Heng Wang
王育��
author Yu-Heng Wang
王育��
spellingShingle Yu-Heng Wang
王育��
Study of the Square Planar Methylpalladium (II) Complexes Bearing Unsymmetrical α-Aminoaldimine Bidentate Ligands of Hetero Functionalities: Synthesis, Geometrical Isomerism and Reactivity
author_sort Yu-Heng Wang
title Study of the Square Planar Methylpalladium (II) Complexes Bearing Unsymmetrical α-Aminoaldimine Bidentate Ligands of Hetero Functionalities: Synthesis, Geometrical Isomerism and Reactivity
title_short Study of the Square Planar Methylpalladium (II) Complexes Bearing Unsymmetrical α-Aminoaldimine Bidentate Ligands of Hetero Functionalities: Synthesis, Geometrical Isomerism and Reactivity
title_full Study of the Square Planar Methylpalladium (II) Complexes Bearing Unsymmetrical α-Aminoaldimine Bidentate Ligands of Hetero Functionalities: Synthesis, Geometrical Isomerism and Reactivity
title_fullStr Study of the Square Planar Methylpalladium (II) Complexes Bearing Unsymmetrical α-Aminoaldimine Bidentate Ligands of Hetero Functionalities: Synthesis, Geometrical Isomerism and Reactivity
title_full_unstemmed Study of the Square Planar Methylpalladium (II) Complexes Bearing Unsymmetrical α-Aminoaldimine Bidentate Ligands of Hetero Functionalities: Synthesis, Geometrical Isomerism and Reactivity
title_sort study of the square planar methylpalladium (ii) complexes bearing unsymmetrical α-aminoaldimine bidentate ligands of hetero functionalities: synthesis, geometrical isomerism and reactivity
url http://ndltd.ncl.edu.tw/handle/69756346158793745913
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