國立僑生大學先修班學報

Permanent URI for this collectionhttp://rportal.lib.ntnu.edu.tw/handle/20.500.12235/217

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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).
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    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).
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    Formation of Organometallic Heterocycles by S-alkylated and N-alkylated Ruthenium Vinylidene Complexes
    (國立僑生大學先修班, 2000-07-??) 張昭苑; Chao-Wan Chang
    Treatment of [Ru]C≡CPh (1 , [Ru] = (η5-C5H5)(dppe)Ru , dppe =Ph2PCH2CH2PPh2 ) with PhN=C=S at room temperature affords the [2 + 2] cycloaddition product [Ru]-C=C(Ph)C(=NPh)S (2) which contains a four-membered heterocycle. A series of cationic S-alkylated ruthenium vinylidene complexes [Ru]=C=C(Ph)C(=NPh)SCH2R+ (3a, R = CONH2 ; 3b, R = CH=CH2 ; 3c, R = p-C 6 H 4 CF 3 ) and N-alkylated ruthenium vinylidene complexes[Ru]=C=C(Ph)C(=S)N(Ph)CH2R+ (4b, R = CH=CH2 ; 4c, R = p-C6H4CF) are prepared from 2 with organic halides at room temperature with high yields.Deprotonation of 3a and 3c by n-Bu4NOH in acetone induces novel cyclization reactions via C-C bond formation and yields neutral five-membered heterocyclic complexes [Ru]-C=C(Ph)C(=NPh)SCHR (5a, R = CONH2; 5c, R = p-C6H4CF3). In a similar manner, deprotonation of 4b and 4c by NaOMe in CH2Cl2 also induces another cyclization to yield the pyrrole-2-thione complexes [Ru]C=C(Ph)C(=S)N(Ph)CHR (6b, R = CH=CH2 ; 6c, R = p-C6H4CF3 ). At room temperature , 5c isomerizes to the 2-aminothiophene complex [Ru]-C=C(P-C6H4CF3)SC(NHPh)=C(Ph) (7c) in solution.