Browsing by Author "張昭菀"

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Cycloaddition and Related Reactions of Ruthenium Acetylide Complexes with EtO2CNCS
(國立僑生大學先修班, 2002-09-??) 張昭菀; Chao-Wan Chang
Treatment of ruthenium acetylide complexes Cp(L)(L')RuC=CPh (la, LL' =dppe, dppe = Ph2PCH2CH2PPh2; lb, L = PPh3, L' = P(Ome)3 with 1.1 equivalent of EtO2CN=C=S at room temperature for one hour results in the [2 + 2] cyc1oaddition to yield the four-membered-ring products Cp(L)(L')Ru-C=C(Ph)C(=NCO2Et)S (2a, LL'=dppe.dppe=Ph2PCH2CH2PPH2;2b,L=PPh3,L'=P(OMe)3).The reaction of complexes 2a and 2b react with 5 fold excess of EtO2CNCS affords the heterocyclic six-membered-ring complexes Cp(L)(L')Ru-C=C(Ph)C(=S)N(CO2Et)C(NCO2Et)S(3a, LL' = dppe, dppe = Ph2PCH2CH2PPh2; 3b, L = PPh3, L' = P(OMe)3). Complex 3a decomposes in excess EtO2CNCS in CH2Cl2 solution to yield a new six-membered-ring complex Cp(dppe)Ru-C=C(Ph)C(SCH2SH)N(=O)O (4). Two molecules of complex 4 in solutions can dimerize into a binuclear complex [Cp(dppe)Ru-C=C(Ph)C(S-)N(=O)O]2CH2 (5).
Electrophilic Reaction of Ruthenium Heterocyclic Six-membered-ring Complexes
(國立僑生大學先修班, 2001-07-??) 張昭菀; Chao-Wan Chang
Treatment of a ruthenium complex with a heterocyclic six-membered-ring ligand Cp(dppe)Ru-C=C(Ph)C(=S)N(Ph)C(=NPh)S (3)with organic halides at room temperature results in the alkylation at the sulfur terminus of the six-membered-ring to yield [Cp(dppe)Ru-C=C(Ph)C(SCH2R)N(Ph)C(=NPh)S][X] (4a, R = CN, X = I; 4b, R = Ph, X = Br; 4c, R=CH=CH2, X=I; 4d, R= p-C6H4CF3, X = Br). The reaction of 3 with HgCl2 affords [Cp(dppe)Ru-C=C(Ph)C(SHgCl)N(Ph)C(=NPh)S][Cl] (5). Further decomposition of 5 in the air gives a cationic vinylidene complex [Cp(dppe)Ru=C=C(Ph)C(O)NHPh]2[Hg2Cl6] (6).
釕金屬乙炔基化合物的反應
(國立僑生大學先修班, 1998-07-??) 張昭菀
將RuCp(PPh3)[ P(OMe)3](-C≡CPh) (1)與有機鹵化物溶於二氯甲烷中反應，並加入六氟瞵化銨(NH4PF 6)作離子交換，會經由NH4PF6中的酸造成酸催化水合反應，生成醢酮化合物RuCp(PPh3)[P(OMe)3]COCH2Ph (2) ，若僅將RuCp(PPh3)[P(OMe)3] (-C≡CPh) (1)與有機鹵化物混合於溶液中反應，不加入NH4PF6，則會進行Arbuzov反應，產生一系列的中性亞乙烯基化合物R uCP(PPh3) [P(O)(OMe)2] [=C=C (Ph)(CH2R)](3a-3d) (R = CN,3a；R = C6F5 , 3b； R = C6H5 , 3c； R = l-C10H 7 ,3d) 。將RuCp(PPh3)[P(OMe)3] (-C≡CPh) (1) 與含不飽和鍵之有機物HPhC=C(CN)2在室溫下作用，可得RuCp(PPh3)[P(OMe)3][-C=C(Ph)-CH(Ph)-C(CN)2] (4) 與RuCp(PPh3)[P(OMe)3] {C[=C(CN)2]-C(Ph)=CH(Ph)} (5) 的混合物以1 : 1 的比例同時生成，將4 與5 在氯仿溶液中加熱迴流，可脫去PPh3配位基，得到化合物RuCp[P(OMe)3] {η3-C[=C(CN)2][C(Ph)=CH(Ph)]} (6) 。若改用HCIC=C(CN)2與1 於室溫下反應，會進行Arbuzov反應，脫去一分子的CH3Cl，而生成中性的亞乙烯基化合物RuCp(PPh3 ) [P(O)(OMe)2][=C=C(Ph)-C(Ph)=C(CN)2] (7) 。將1與(CH3)3SiN3反應，生成化合物{RuCp(PPh3)[P(OMe)3](NCCH2Ph)+}(N3-) (8) ，用NH4PF6與其作離子交換，可得到穩定的{RuCp(PPh3)[P(OMe)3] (NCCH2Ph+}(PF6-)。文中並附有化合物2的晶體構造資料。
釕金屬亞乙烯基化合物的合成及晶體構造分析
(國立僑生大學先修班, 1997-07-??) 張昭菀
以Cp(dppe)RuC1(1b)合成n1-乙炔基化合物Cp(dppe)Ru-C≡C-ph(4)時，會有trans-RuCl2(2)、[RuClCp(u-dppe)]2(3)兩種副產物同時生成。將n1-乙炔基化合物Cp(dppe)Ru-C≡C-ph(4)與一系列親電子性試劑XCH2R作用可得到Cr上含拉電子基的釕金屬亞乙烯基化合物，[Cp(dppe)Ru=C=C(ph)(Ch2R)]﹝X﹞(5a~5g)(R=CN，5a；C6F5，5b；C6H5，5c；p-C6H4CN，5d；p-C6H4CF3，5e；CO2CH3，5g；X=Br or I)。其中2、3、5a、5c、5e可養晶得晶體構造資料。本文中並探討亞乙烯基化合物的物理及化學性質。