過渡金屬鹵化物之巨分子化學

Supramolecular Chemistry of Transition Metal Halide Complexes

劉淑惠(Shu-Hui Liu)

指導教授 ： 陳志德

中原大學/理學院/化學研究所/碩士(2001年)

https://doi.org/10.6840/cycu200100156

摘要

中文摘要

本論主要探討過渡金屬鹵化物之巨分子化學研究。此類化合物結構已用單晶X-ray鑑定出，結構特性則利用FT-IR與1H-NMR光譜鑑定，並以熱重量分析(TGA)和微差熱掃瞄卡計(DSC)儀器測試瞭解其熱性質。
第一部分：探討以2-胺基吡啶配位基與鉑、銅、錫、汞和鈀二價金屬鹵化合物。新化合物之分子式為[H(2-ampy)]2[PtCl4]，1 [H(2-ampy)]2[CuCl4]，2 [H(2-ampy)]2[SnCl6]，3 [H(2-ampy)]4[Hg2Cl6]，4 [H(2-ampy)]2[PdCl4]，5 (2-ampy = 2-Aminopyridine)。論文將提及一特殊之四中心氫鍵(有三叉)的Pt(Ⅱ)化合物1，其具有一個Npyridine-H---Pt和兩個Npyridine-H---Cl相互作用和四中心的氯原子特殊連接現象。化合物3則同時具有Sn-Cl---H2和Sn-Cl---H3型式的三中心和四中心之氫鍵(2.562 ~ 2.902 Å)，更伴隨重要的金屬層和[H(2-ampy)]+陽離子分層交叉連繫。化合物4 則有別於其它陰離子，形成特殊的edge-sharing bitetahedron [Hg2Cl6]2-之陰離子鏈。化合物1 ~ 5形式中質子化的2-胺基吡啶皆經由Npyridine-H---X，Namine-H---X和C-H---X氫鍵相互作用，能交錯連結金屬鹵化物形成片狀分子。在此[H(2-ampy)]+陽離子對於控制金屬離子是否交叉之作用方式扮演重要的角色，也已被廣泛的討論。
第二部分：探討以2,6-二胺基吡啶配位基與錫、鎘、汞和銅二價金屬化合物。新化合物之分子式為[H(2,6-diampy)]2[SnCl6]，6 [H(2,6-diampy)][CdCl3]，7 [H(2,6-diampy)]6{[Hg2Cl6][HgCl4]2}，8 [H(2,6-diampy)][CuBr2]，9 [H(2,6-diampyBr)]3[CuBr4]，10 (2,6-diampy = 2,6-Diaminopyridine)結構已用單晶X-ray鑑定出。從整個化合物結構解析中，得知皆為一價之質子化二胺基吡啶陽離子和不同價數之過渡金屬鹵陰離子或陰離子聚合體鏈所組成。不變的是彼此間仍運用Npyridine-H---X，Namine-H---X和C-H---X (X = Cl, Br)相互作用形成多變化的氫鍵連接成巨分子型態。化合物6結構中特色是可觀測到Npyridine-H---Cl2和Sn-Cl---H2兩種三中心的鍵結模式。另一特點是化合物7 ~ 9之陰離子部分形成edge-sharing bitetrahedron聚合體鏈。化合物8, 9的形成是同樣使用CuBr2 ·6H2O和2,6-diampy混合並用氫溴酸溶解反應，所產生兩種不同晶體結構，一為無色單質子體(C5H7N3Br)CuBr4，8和黑褐色聚合體鏈(C5H8N3)CuBr2，9。化合物8包含一獨立的正四面體陰離子[CuBr]3-，並以多個的Npyridine-H---Br，Namine-H---Br和C-H---Br氫鍵穩定其結構。最初2,6-二胺基吡啶與二價溴化銅在合成程序中，部分遭受到溴化反應的影響，致使化合物中伴隨著二價銅還原成一價銅離子化物。化合物9是經由一價銅金屬為中心，雙重地edge-sharing及透過溴原子的連接組成陰離子鏈。線性鏈{[CuBr2]n}n- 經由Npyridine-H---Br和Namine-H---Br (2.582 ~ 2.951 Å)連接而相互作用形成二維分子片狀化合物。
第三部分：探討以R-(+)-α-甲基苯甲基胺和S-(-)-α-甲基苯甲基胺配位基與錫、鎘、汞和銅二價金屬化合物。新化合物之分子式為[H(R-mba)]2[CuCl4]，11 [H(S-mba)]2[CuCl4]，12 (R-mba = R-(+)-α-Methylbenzylamine；S-mba = S-(-)-α-Methylbenzylamine)。從整個化合物結構解析中，得知皆為一價之質子化之R-(+)-α-甲基苯甲基胺、S-(-)-α-甲基苯甲基胺配位基陽離子，和二價之過渡金屬鹵陰離子所組成。最重要的是彼此間也運用Npyridine-H---Cl和Namine-H---Cl相互作用形成多變化的氫鍵連接成巨分子型態，也形成了三中心氫鍵(2.409 ~ 2.812 Å)。

關鍵字

R-(+)-α-甲基苯甲基胺 ； 2-胺基吡啶 ； 氫鍵 ； 2，6-二胺基吡啶 ； S-(-)-α-甲基苯甲基胺

並列摘要

Abstract

This thesis discusses the supramolecular chemistry of transition metal halide complexes, which have been determined by X-ray crystallography and characterized by FT-IR, 1H-NMR, TGA and DSC.
The complexes [H(2-ampy)]2[PtCl4] 1, [H(2-ampy)]2[CuCl4] 2, [H(2-ampy)]2[SnCl6] 3, [H(2-ampy)]4[Hg2Cl6]2 4, and [H(2-ampy)]2[PdCl4] 5 (2-ampy = 2-Aminopyridine) were prepared by reactions of 2-aminopyridine with appropriate metal halide in HCl. An unprecedented four-center (trifurcated) hydrogen bond involving two Npyridine-H---Cl and one Npyridine-H---Pt interactions was found in complex 1. In complex 3, both three-center and four-center hydrogen bonding of the types Sn-Cl---H2 and Sn-Cl---H3 were observed, which are important in cross-linking the metal layers and the [H(2-ampy)]+ cations. Complex 4 contains doubly edge-sharing bitetrahedral [Hg2Cl6]2- anions, which form linear chains through weak Hg---Cl interactions. The structural role of [H(2-ampy)]+ in these complexes to control the aggregation of the metal ions is discussed.
The complexes [H(2,6-diampy)]2[SnCl6] 6, [H(2,6-diampy)]6{[Hg2Cl6][HgCl4]2} 7, [H(2,6-diampyBr)]3[CuBr4] 8, [H(2,6-diampy)]2[CuBr2] 9, [H(2,6-diampy)][CdCl3] 10 (2,6-diampy = 2,6-diaminopyridine) were prepared by reaction of 2,6-diaminopyridine with appropriate metal halide in HCl or HBr. In these structures, various types of hydrogen bonds are used to create larger molecular arrays. Most importantly, Npyridine-H---X and Namine-H---X (X = Cl, Br) interactions are used to link the metal units to the protonated 2,6-Diaminopyridine. In complex 6, both three-center and four-center hydrogen bonding of the types Npyridine-H---Cl2, Namine-H---Cl2 and Sn-Cl---H2 are observed. Complex 7 contains two isolated [HgCl4]2- and one [HgCl4]2- anions, in which the [HgCl4]2- anions are edge-sharing with [HgCl4]2- to form a linear tetranuclear complexes through weak Hg---Cl interactions. Complex 8 contains a unique, isolated tetrahedral [CuBr4]3- anion, which is stabilized by extensive Npyridine-H---Br, Namine-H---Br and C-H---Br hydrogen bonding. The pyridine rings of the original 2,6-diaminopyridine compounds have undergone bromoation during the synthesis process and was accompanied by reduction of the Cu(II) ion to Cu(I). The structure of 9 consists of anionic chains of doubly edge-sharing copper (I) metal centers through bromide atoms. The {[CuBr2]n}n- linear chains are linked into two-dimensional molecular sheets through the Npyridine-H---Br and Namine-H---Br interactions (2.582 to 2.951 Å).
The complexes [H(R-mba)]2[CuCl4] 11, [H(S-mba)]2[CuCl4] 12, (R-mba = R-(+)-α-Methylbenzylamine; S-mba = S-(-)-α-Methylbenzylamine) were prepared by reactions of CuCl2 with R-mba and S-mba, respectively, in HCl. In these complexes Npyridine-H---Cl and Namine-H---Cl interactions are used to link the metal units to the protonated R-(+)-α-Methylbenzylamine and S-(-)-α-Methylbenzylamine. Both three-center hydrogen bondings were observed in the complexes.

並列關鍵字

2，6-Diaminopyridine ； S-(-)-α-Methylbenzylamine ； Hydrogen bond ； R-(+)-α-Methylbenzylamine ； 2-Aminopyridine

參考文獻

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