胺基-吡啶雙牙配位基的電子效應在平面甲基鈀的幾何異構物及其烯烴共聚合反應的研究

Study of the Electronic Effect to the Olefin Copolymerization and Geometrical Isomerism with respect to Methylpalladium(II) Complexes Bearing α-Amino-pyridine Lignads

游國軒(Kuo-Hsuan Yu)

指導教授 ： 陳竹亭

國立臺灣大學/理學院/化學研究所/碩士(2007年)

https://doi.org/10.6342/NTU.2007.01248

摘要

一系列在胺基上帶有不同取代基的胺基-吡啶雙牙配位基以(C5H5N)CH(R1)NH(R2)形式 (R1=甲基、R2 =對-N,N-二甲氨基苯基(LH-a)、對甲氧基苯基(LH-b)、對甲苯基(LH-c)、苯基(LH-d)、對氟苯基(LH-e)、對氯苯基(LH-f)、硝基苯基(LH-g)、鄰甲苯基(LH-h)、2,4,6-三甲基苯基(LH-i)、環己基(LH-k)；R1=氫、R2 =2,4,6-三甲基苯基(LH-j))成功的被合成出來，這些不同的衍生物是用來探討配位基的電子效應在中性與陽離子鈀金屬錯合物(Pd(L)MeCl; [Pd(L)Me(MeCN)]BF4)上的影響，藉由X光單晶繞射與NMR鑑定，中性與陽離子鈀錯合物的1H與13C NMR化學位移和C≡N紅外線光譜頻率都與取代基的Hammett取代常數有強烈的關聯，而這平面四邊形的鈀金屬錯合物包含兩種幾何異構物，分別是順式和反式異構物，幾何異構物的比例也與Hammett取代常數有明顯的相關，推電子的取代基會穩定反式異構物，提高其異構物的比例。
陽離子的[Pd(LH)Me(MeCN)]BF4錯合物能夠進行乙烯與降冰片烯的共聚合反應活性約在5×103至9×104 g(COC)/mol Pd

關鍵字

電子效應 ； 胺基-吡啶 ； 鈀 ； 共聚合 ； 乙烯 ； 降冰片烯

並列摘要

A series of α-aminopyridine ligands bearing different substituted group on the amine in the form of (C5H5N)CH(R1)NH(R2) (R1 = Me, R2 = p-N,N-dimethylaminophenyl(LH-a), p-methoxyphenyl(LH-b), p-methylphenyl(LH-c), phenyl(LH-d), p-fluoropheny(LH-e), p-chlorophenyl(LH-f), p-nitrophenyl(LH-g), o-methylphenyl(LH-h), 2,4,6-trimethylphenyl(LH-i), cyclohexyl(LH-k); R1 = H, R2 = 2,4,6-trimethylphenyl(LH-j)) were synthesized. Such derivatives are prepared to systematically investigate the ligand electronic effect to neutral organopalladium(II) complexes in the form of (LH)Pd(Me)Cl and the cationic derivatives in the form of [(LH)Pd(Me)(NCMe)]BF4. The prepared complexes were characterized by the NMR techniques and X-ray crystallography. 1H and 13C NMR chemical shifts and C≡N stretching frequencies of the neutral and cationic complexes were found to correlate strongly with the Hammett substituent constant (σp) of the substituent on the ligand. The square planar geometry of these species results in cis- and trans- isomers. The relative yields of the geometrical isomers exhibit significant correlation with the Hammett substituent constants (σp) of the substituent on the ligand. The electron-donating ligands appear to stabilize the isomers of cis form.
The cationic [Pd(LH)Me(MeCN)]BF4 complexes catalyze copolymerization of ethylene and norbornene with the activities of 5×103 ~ 9×104 g(COC)/mol Pd

並列關鍵字

electronic effect ； amino-pyridine ； palladium ； copolymerization ； ethylene ； norbornene

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