磷橋異核雙金屬錯合物的配位子移轉

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鄧青棋(Deng Ching-Chi) 查詢紙本館藏

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化學學系

論文名稱

磷橋異核雙金屬錯合物的配位子移轉
(Ligand Migration on Phosphido-Bridged Heterobimetallic Complexes)

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摘要(中)

本篇論文主旨在於觀察雙金屬錯合物的配子移轉。藉著環戊二烯的第6族單金屬錯合物CpMPPh2 (M= Cr, Mo, W)與釕金屬錯合物Ru(PPh3)3Cl2在室溫下進行反應，反應過後羰基、氯配位子會在釕金屬和第6族金屬之間移轉，我們可以得到磷橋異核雙金屬錯合物Cp(CO)(Cl)W(μ-PPh2)(μ-Cl)Ru-
(CO)2(PPh3) (1)和Cp(CO)(Cl)Mo(μ-PPh2)(μ-Cl)Ru(CO)2(PPh3) (2)，錯合物1和2之晶體結構是由X光單晶繞射決定。1的W-Ru鍵距為2.8189(16)Å，表示W-Ru金屬鍵存在。2的Mo-Ru鍵距為2.8145(10) Å，表示Mo-Ru金屬鍵存在。而在類似的反應條件下，Na[W(CO)3Cp]、氯化二苯磷、氯化二苯磷氧化物與釕金屬錯合物Ru(PPh3)3Cl2在室溫下進行反應會得到錯合物1和錯合物Cp(CO)W(μ-PPh2)(μ-OPPh2)(μ-Cl)Ru(CO)(PPh3) (3a)和(3b)，錯合物3a和3b之晶體結構是由X光單晶繞射決定。錯合物3a的氯化二苯磷氧化物配位基上的磷原子是接到W上，而氧原子則是接到Ru上，3a的W-Ru鍵距為2.7359(8) Å，表示W-Ru金屬鍵存在。錯合物3b的氯化二苯磷氧化物配位基上的氧原子是接到W上，而磷原子則是接到Ru上。

摘要(英)

The cyclopentadiene transition metal complexes (CpW(CO)3PPh2 and CpMo(CO)3PPh2) can react with Ru(PPh3)3Cl2 in tetrahydrofuran at room temperature. These reactions produced phosphido-bridged heterobimetallic complexes Cp(CO)(Cl)W(μ-PPh2)(μ-Cl)Ru(CO)2(PPh3) (1) and Cp(CO)(Cl)Mo(μ-PPh2)(μ-Cl)Ru(CO)2(PPh3) (2) in high yield. The chloride and carbonyl ligands migrated irreversibly between Ru and d6 transition metals (Mo and W) in 1 and 2. In similar reaction conditions, Na[W(CO)3Cp] and chlorodiphenylphosphine and chlorodiphenylphosphine oxide can react with Ru(PPh3)3Cl2 and afforded two isomers (3a and 3b) of Cp(CO)W(μ-PPh2)-
(μ-OPPh2)(μ-Cl)Ru(CO)(PPh3). The bridging chlorodiphenylphosphine oxide group is oxygen-bound to Ru and phosphorus-bound to W in 3a but the bonding of phosphorus and oxygen of chlorodiphenylphosphine oxide towards W and Ru in 3b is reverse.

關鍵字(中)

★ 流變
★ 配位子移轉
★ 錯合物
★ 雙金屬
★ 異核
★ 磷橋

關鍵字(英)

★ Heterobimetallic Complexes
★ Phosphido-Bridged
★ Ligand Migration

論文目次

誌謝辭....................................................................................................................i
中文摘要...............................................................................................................ii
英文摘要..............................................................................................................iii
目錄......................................................................................................................iv
圖目錄..................................................................................................................vi
表目錄................................................................................................................viii
第一章緒論.........................................................................................................1
第二章實驗.......................................................................................................12
2-1 儀器....................................................................................................12
2-2 試劑與試藥處理…............................................................................12
2-3 Na[W(CO)3Cp]、氯化二苯磷、氯化二苯磷氧化物與RuCl2(PPh3)3之反應.................................................................................................................14
2-4 CpW(CO)3PPh2與RuCl2(PPh3)3之反應............................................16
2-5 CpMo(CO)3PPh2與RuCl2(PPh3)3之反應..........................................17
2-6 CpCr(CO)3PPh2與RuCl2(PPh3)3之反應...........................................18
2-7 觀察錯合物1升溫時能否進行配位子.............................................18
2-8 CpMo(CO)3PPh2與RuCl2(PPh3)3之31P{1H} NMR監控反應.........19
2-9 Na[M(CO)3Cp] (M= W, Mo, Cr)、氯化二苯磷氧化物與RuCl2(PPh3)3之反應...........................................................................................19
2-10 X-ray 單晶繞射(結構解析)............................................................20
第三章結果與討論...........................................................................................21
3-1 錯合物1的合成，光譜特性和錯合物結構.......................................21
3-2 錯合物1, 3a和3b的結構由X-ray單晶繞射決定...........................27
3-3 錯合物1和3b的升溫反應與31P{1H} NMR光譜變化....................31
3-4 錯合物2的合成，光譜特性和錯合物結構.......................................31
3-5 錯合物2的結構由X-ray單晶繞射決定..........................................35
3-6 CpCr(CO)3PPh2與Ru(PPh3)3Cl2進行反應.......................................39
3-7 Na[W(CO)3Cp]、氯化二苯磷、氯化二苯磷氧化物與RuCl2(PPh3)3之反應.................................................................................................................39
第四章結論.......................................................................................................40
參考文獻.............................................................................................................41
附錄一(IR 光譜)................................................................................................44
附錄二(NMR 光譜)...........................................................................................45
附錄三.................................................................................................................57

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指導教授

李光華、徐新光
(Kwang-Hwa Lii、Shin-Guang Shyu)

審核日期

2009-7-20

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