雙核金屬(Cu,Ag)與二硫(硒)磷酸配位基反應性的比較

林雅雯

3.237.66.86，Hello！

Close
Search Quick Search Advanced Search Publication Search	Personal Service Member Login Searching History Use Bonus Card SYMSKAN
Browse Browse by University of Graduate Thesis Browse by Pinyin of Graduate Thesis Browse by Conference Proceedings Topic Browse by Conference Proceedings Publisher Browse by Pinyin of Conference Proceedings Browse by eBook Category Browse by eBook Topic Browse by eBook Publisher
Customer Services Authorize Airiti Recommend a Journal

Search Symbol (Half-width)	Description of Search Symbols
Space	"AND" indicates the intertwining of key terms used in a search
Double Quotation Marks ("") ( " " )	Double quotation marks indicate the beginning and end of a phrase, and the search will only include terms that appear in the same order of those within the quotations. Example: "image process" ： " image process "
?	Indicates a variable letter. Entering two ? will indicate two variable letters, and so on. Example: "Appl?", search results will yield apple, apply… e , appl y … ( (often used to English word searches) )
*	Indicates an unlimited number of variable letters to follow, from 1~n. Example: Enter "appl*", search results will yield apple, apples, apply, applied, application…(often used in English word searches) e , appl es , appl y , appl ied , appl ication … ( (often used to English word searches) )
AND、OR、NOT	Boolean logic combinations of key words is a skill used to expand or refine search parameters. (1) AND (1) AND: Refines search parameters (2) OR (2) OR: Expands search parameters (3) NOT: Excludes irrelevant parameters

DOI stands for Digital Object Identifier （ D igital O bject I dentifier ） ,
and is the unique identifier for objects on the internet. It can be used to create persistent link and to cite articles.

Using DOI as a persistent link

To create a persistent link, add「http://dx.doi.org/」「 http://dx.doi.org/ 」 before a DOI.
For instance, if the DOI of an article is 10.5297/ser.1201.002 , you can link persistently to the article by entering the following link in your browser: http://dx.doi.org/ 10.5297/ser.1201.002 。
The DOI link will always direct you to the most updated article page no matter how the publisher changes the document's position, avoiding errors when engaging in important research.

Cite a document with DOI

When citing references, you should also cite the DOI if the article has one. If your citation guideline does not include DOIs, you may cite the DOI link.

DOIs allow accurate citations, improve academic contents connections, and allow users to gain better experience across different platforms. Currently, there are more than 70 million DOIs registered for academic contents. If you want to understand more about DOI, please visit airiti DOI Registration （ doi.airiti.com ）。

Data Source

Basic & Applied Sciences > Chemistry
College of Science > Graduate Institute of Chemistry

Bibliography Management Tool

Related Links

Report an Issue

Search in Library

There is no full-text available at the moment. Airiti would like to request author's authorization. I would like to provide authorization.

雙核金屬(Cu,Ag)與二硫(硒)磷酸配位基反應性的比較

A Distinct Reactivity Between Dithiophosphates and Diselenophosphates With Dinuclear Metal complexes ( M = Cu，Ag )

林雅雯 , Masters　　Advisor：劉鎮維　　

繁體中文

二硒磷酸配位基；晶體結構；二硫磷酸配位基；雙核金屬錯合物； Dinuclear Metal complexes ； crystall structure ； diselenophosphate ； dithiophosphate

Abstract │ Reference (51) │ Altmetrics

Abstract 〈TOP〉

中文摘要
本篇論文主要是討論 dtp 配位基和 dsep 配位基與 [M2(-dppm)2(CH3CN)2][PF6]2 (M = Cu, Ag) 反應性的不同。
利用dtp 配位基與 [M2(-dppm)2(CH3CN)2][PF6]2 (M = Cu, Ag) 反應後得到以螯合模式鍵結的 [Cu2(-dppm)2(S2P(OR)2)2] (R = Et, 2; iPr, 1)、[Ag2(-dppm)2(S2P(OR)2)2] (R = iPr, 7)，架橋模式鍵結的 [Ag4(-dppm)2(S2P(OR)2)4] (R = Et, 4; iPr, 6) 和懸掛式鍵結的 [Ag3(-dppm)3(S2P(OR)2)2][PF6] (R = Et, 5)。
當我們將雙核金屬起始物改為利用單核金屬與 dppm 分別加入的方式反應發現，在 Cu 的部分得到相同結果的 [Cu2(-dppm)2(S2P(OR)2)2] (R = Et, 2; iPr, 1)，而在 Ag 的部分則只得到 [Ag4(-dppm)2(S2P(OR)2)4] (R = Et, 4; iPr, 6)的產物。
 有趣的是當我們加入 dsep 配位基，配位基上的 Se 原子會被三配位的P打斷，其化合物為[M(SePPh2CH2PPh2)2][PF6] (M = CuⅠ,3; AgⅠ, 8)，這個結果讓我們知道 P-Se 比 P-S 的鍵來的弱。而且他們的 31P NMR 圖譜較特別的是包含了 3J 的耦合，使得圖譜看起來更為複雜。
下列為化合物1, 3, 4, 5, 6, 和8 簡單的晶體資料：
1,orthorhomic, Pbcn, Z = 4, a = 18.5658(11)Å, b = 15.5449(9) Å, c = 24.486(2) Å, V = 7078.3(7) Å3, R1 = 0.0474, wR2 = 0.1311; 3, orthorhomic, P21212, Z = 4, a =20.5638(11) Å, b = 39.594(2) Å, c = 11.9181(6) Å, V = 9694.2(9) Å3, R1 = 0.0472, wR2 = 0.0939; 4, monoclinic, P21/n, Z = 4, a = 14.1504(11)Å, b = 17.8787(13) Å, c = 16.4680(10) Å, V = 4165.9 (5) Å3, R1 = 0.0358, wR2 = 0.0936; 5, orthorhomic, Pna21, Z = 4, a = 32.200(2)Å, b = 18.5101(9) Å, c = 14.5405(7) Å, V = 8666.6 (7) Å3, R1 = 0.0366, wR2 = 0.0930; 6, Orthorhomic, Pbca, Z = 4, a = 17.2672(17)Å, b = 22.7228(17) Å, c = 23.462(2) Å, V = 9205.5 (14) Å3, R1 = 0.0660, wR2 = 0.1478; 8, orthorhomic, Pcca, Z = 4, a = 20.9126(12)Å, b = 11.9598(7) Å, c = 19.6907(12) Å, V = 4924.9 (5) Å3, R1 = 0.0665, wR2 = 0.1306

Parallel Abstract 〈TOP〉

Abstract 
The main theme of this thesis focuses on the reactivity between the reaction of dialkyl dithiophosphate (dtp) and dialkyl diselenophosphate (dsep) with monovalent copper and silver complexes.
While the reaction of NH4S2P(OR)2 and [Cu2(徭ppm)2(CH3CN)2] [PF6]2 affords [Cu(-dppm)2(S2P(OR)2)2] (R = Et, 2; iPr, 1), the analogous reaction of Ag produces [Ag4(-dppm)2(S2P(OR)2)4] (R = Et, 4; iPr, 6), [Ag3(-dppm)3(S2P(OR)2)2][PF6] (R = Et, 5) and [Ag2(-dppm)2(S2P(OiPr)2)2], 7.  In complexes 1, 2, and 7, a simple chelated bonding mode is observed for the dtp ligands.  In cationic, trinuclear silver cage, 5, each edge of the Ag3 plane is bridged by a dppm ligand with the dtp ligands in an unusual bridged-dangling conformation for the two sulfur atoms.  As a result, two of the silver atoms in 5 are trigonally coordinated by two P atoms and one S atom.  Interestingly, the bonding modes of the dtp ligands for clusters 4 and 6 are also different.  Whereas a bridged-chelated pattern for dtp is observed in 4, a bridged-dangling connective pattern is found in two of four dtp in 6.  Surprisingly, a one-pot reaction of Ag(CH2CN)4PF6, NH4S2P(OR)2, and dppm produces tetranuclear clusters solely.
When the dialkyl diselenophosphate ligands where incorporated in the reaction, the selsnium atoms abstracted by the tertiary phosphines are uncoverd and compounds of the type, M(SePPh2CH2PPh2)2(PF6), (M = Cu, 3; Ag, 8) are isolated.  The intriguing 31P-NMR spectra for these mononuclear compounds are also presented.
  Pertinent crytallographic date for 1, 3, 4, 5, 6, and 8 are following:
1,orthorhomic, Pbcn, Z = 4, a = 18.5658(11)Å, b = 15.5449(9) Å, c = 24.486(2) Å, V = 7078.3(7) Å3, R1= 0.0474, wR2 = 0.1311; 3, orthorhomic, P21212, Z = 4, a =20.5638(11) Å, b = 39.594(2) Å, c = 11.9181(6) Å, V = 9694.2(9) Å3, R1= 0.0472, wR2 = 0.0939; 4, monoclinic, P21/n, Z = 4, a = 14.1504(11)Å, b = 17.8787(13) Å, c = 16.4680(10) Å, V = 4165.9 (5) Å3, R1= 0.0358, wR2 = 0.0936; 5, orthorhomic, Pna21, Z = 4, a = 32.200(2)Å, b = 18.5101(9) Å, c = 14.5405(7) Å, V = 8666.6 (7) Å3, R1 = 0.0366, wR2 = 0.0930; 6, orthorhomic, Pbca, Z = 4, a = 17.2672(17)Å, b = 22.7228(17) Å, c = 23.462(2) Å, V = 9205.5 (14) Å3, R1 = 0.0660, wR2 = 0.1478; 8, orthorhomic, Pcca, Z = 4, a = 20.9126(12)Å, b = 11.9598(7) Å, c = 19.6907(12) Å, V = 4924.9 (5) Å3, R1= 0.0665, Rw2= 0.1306

Reference ( 51 ) 〈TOP〉

6. Matsumoto Keiji; Tanaka Rika; Nakaom Yasuo; Inorg. Chim. Acta 2000, 304, 293-296
連結：
7. Liu C. W.; Chen Hsiu-Chih; Wang Ju-Chung; Keng Tai-Chiun, Chem. Commun. ,1998, 1831
連結：
8. Liu C. W.; Hung, C.-M.; Chen, H.-C.; Wang, J.-C.; Keng, T.-C.; Guo, K., Chem. Commun., 2000, 1897
連結：
15. Churchill, M. R.; Kalra, K. L., Inorg. Chem., 1974, 13, 1065
連結：
16. Theivanayagam, C.; Deivaraj ; Vittal, J. J., J. Chem. Soc., Dalton Trans., 2001, 329-335
連結：

Altmetrics

〈TOP〉

E-mail ：

When an article is available to download, a notice will be sent to your mailbox address.

E-mail ：