修飾萘啶胺配基及其釕金屬與異核金屬串錯合物之合成與研究

Syntheses and Studies of Ruthenium and Heterometallic Metal String Complexes with Modified Naphthylridylamide Ligands

蔡承孝(Cherng-Shiaw Tsai)

指導教授 ： 彭旭明

國立臺灣大學/理學院/化學研究所/博士(2014年)

https://doi.org/10.6342/NTU.2014.00272

摘要

本論文主要是以萘啶胺作為基礎，再修飾苯環或是萘取代基後所得到的兩個配基：2-phenylamino-1,8-naphthyridine (Hphany)與2-naphthylamino- 1,8-naphthyridine (Hnaany)，再藉著這兩個配基與金屬離子反應後而得到一系列同金屬、異金屬三核金屬串錯合物，包含：(4,0)-[Ni3(phany)4Cl][PF6] (1)、(4,0)-[Ni3(naany)4Cl][PF6] (2)、(3,1)-[Ru3(phany)4(NCS)2][PF6] (3)、 (4,0)-[Ni2Pd(phany)4Cl][PF6] (4)、(2,2)-trans-[Mo2Ni(phany)4(NCS)2] (5)、(2,2)-trans-[Mo2Co(phany)4(NCS)2] (6)、(3,1)-[Mo2Ni(phany)4(NCS)2] (7)、(3,1)-[Mo2Ni(phany)4(NCS)2][PF6] (8)、(3,1)-[Mo2Co(phany)4(NCS)2] (9)及(3,1)-[Mo2Co(phany)4F2][PF6] (10)，並對這些化合物做合成、結構及相關的性質探討。
在化合物1、2中藉著軸向的氯離子與這兩種配基末端的phenyl及naphthaly取代基的立體障礙影響，我們成功的以空間效應來促使這兩個金屬錯合物形成單一的(4,0)-form異構物。而從結構與相關性質量測的結果可以發現，這兩個取代基並不會對所生成金屬串的相關性質產生影響。
化合物3則是以釕金屬作為骨幹的稀有第二列過渡金屬串錯合物。從結構上發現，化合物3基於Jahn-Teller效應的影響，此化合物內金屬離子的鍵角為170.26°；且藉著DFT計算得知，被硫氰酸根所穩定而半填滿的π*軌域，會使金屬金屬間的距離增加。
在化合物4的合成中，同樣是藉著較大的氯離子作為軸向配基，而促使化合物生成(4,0)-form的產物。同時也藉由不對稱配基上氮的配位能力差異，使鈀離子配位在胺基上而鎳離子則鍵結在萘啶上，成功的得到了一個未失序的結構排列。從結構上的資訊得知，僅有配位上軸向配基的鎳離子為高自旋的電子組態，這也與磁性分析相吻合。
化合物5與化合物6係利用一鍋法將鉬起始物(Mo2OAc4)與鎳或鈷離子同時反應後再藉著管住層析分離所得到；兩個化合物藉著單晶結構的解析後確認皆為(2,2)-trans-form的金屬串錯合物。儘管使用了雙核的Mo2起始物以及不對稱的配基Hphany，但是這兩個化合物的三個金屬還是有失序的現象。
化合物7的合成方式與化合物5相同，但除了初次合成時有發現化合物5的生成，爾後的實驗中並沒有發現化合物5的出現。化合物7在結構的解析當中並無失序的行為；因為配位上較強場的硫氰酸根，而使得Mo-Mo的鍵長較一般的四重鍵來的稍長。由結構上看來，僅有鎳離子為高自旋S = 1的電子組態，這也與磁性結果相符。藉著氧化劑FcPF¬6的作用下，我們可以得到單一電子氧化的化合物8。從結構上看來氧化後的Mo(2)-Namide鍵長會比中性的化合物7短一點，且Mo-Mo的鍵長也比中性化合物長一些。由這兩個結構上的證據以及磁性量測的結果我們推斷氧化應該是發生在Mo2單元上。
同樣是(3,1)-form的異核金屬串化合物9，其結構與化合物7類似，且並無結晶學上失序的情形。雙核的鉬金屬間以四重鍵連結，而鈷離子則為高自旋S = 3/2的電子組態。氧化之後所得到的化合物10，其軸向配基被置換為氟離子；而由結構上的推斷，我們認為氧化可能是發生在鈷離子上。

關鍵字

釕金屬串 ； 異核金屬串 ； 萘啶

並列摘要

Using 2-Phenylamino-1,8-naphthyridine (Hphany) or 2-Naphthylamino-1,8- naphthyridine (Hnaany) as organic ligands with different transition metal ions, we obtained a series of homo- and heteronuclear metal string complexes, including (4,0)-[Ni3(phany)4Cl][PF6] (1), (4,0)-[Ni3(naany)4Cl][PF6] (2), (3,1)-[Ru3(phany)4(NCS)2][PF6] (3), (4,0)-[Ni2Pd(phany)4Cl][PF6] (4), (2,2)-trans-[Mo2Ni(phany)4(NCS)2] (5), (2,2)-trans-[Mo2Co(phany)4(NCS)2] (6), (3,1)-[Mo2Ni(phany)4(NCS)2] (7), (3,1)-[Mo2Ni(phany)4(NCS)2][PF6] (8), (3,1)-[Mo2Co(phany)4(NCS)2] (9), and (3,1)-[Mo2Co(phany)4F2][PF6] (10). This dissertation is presented to study the crystal structures and the physical properties of these string complexes.
By the steric effect of terminal chloride ions and bulky phenyl and naphthyl group, compounds 1 and 2 adopt a unique (4,0)-form arrangement. And these two different substituents do not affect related properties of the resulting compounds.
X-ray single-crystal analysis shows that compound 3 exhibits a nonlinear [Ru3]7+ backbone with long Ru-Ru bond lengths. The long Ru-Ru distances observed for 3 decrease the Ru-Ru interactions and electric conductance. Magnetic measurements indicate that compound 3 is in S = ½ state. DFT calculations suggest that this unpaired electron occupies the π* orbital which is stabilized by π-acid NCS－ ligands and thus weakening the Ru-Ru π interaction.
In the synthesis of this heteronuclear compound 4, we also get pure (4,0)-form isomer by the steric hindrance of terminal chloride and phenyl group. By the coordination ability of these nitrogen atoms of this unsymmetrical Hphany ligand, we can obtain a crystallographic ordered metal arrangement.
By the one-pot synthesis and column chromatography purification, we can get compound 5 and 6. Despite using Mo2(OAc)4 as a starting material and the unsymmetrical Hphany ligand, the metal ions in these two compounds are crystallographic disordered.
With the same synthetic procedure of compound 5, we can get this thermodynamic stable compound 7. The crystal structure of this compound is well characterized, and the Mo-Mo bond distance is slightly longer than common quadruple bonding. After treatment with an oxidizing agent FcPF6, we obtain an one-electron oxidized compound 8. Due to the removal of bonding electron of Mo2 unit, the Mo-Mo bond distance is slightly longer than neutral one, and the Mo-N distances become shorter. The neutral compound 7 exhibits paramagnetic magnetism and the oxidized compound 8 shows a weak antiferromagnetic coupling.
The structure of compound 9 is similar to compound 7, and the only terminal cobalt ion is high spin electronic configuration (S = 3/2). After treatment with an oxidizing agent FcPF6, we can also obtain an oxidized compound 10. By the result of structure determination, we confirm that the oxidized reaction take place at the Co ion.

並列關鍵字

EMACs ； Ruthenium Metal String Complex ； Heterometallic String Complexe

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