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    Please use this identifier to cite or link to this item: http://ir.lib.ncu.edu.tw/handle/987654321/6522


    Title: 磷橋異核雙金屬錯合物的配位子移轉;Ligand Migration on Phosphido-Bridged Heterobimetallic Complexes
    Authors: 鄧青棋;Deng Ching-Chi
    Contributors: 化學研究所
    Keywords: 流變;配位子移轉;錯合物;雙金屬;異核;磷橋;Heterobimetallic Complexes;Phosphido-Bridged;Ligand Migration
    Date: 2009-06-31
    Issue Date: 2009-09-22 10:21:04 (UTC+8)
    Publisher: 國立中央大學圖書館
    Abstract: 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。 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.
    Appears in Collections:[化學研究所] 博碩士論文

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