本論文分為兩個部分:第一部分主要利用釕金屬鹵化錯合物與末 端炔類進行反應,產生非預期的產物,其產物皆經由亞乙烯基化合物 為中間體而產生,我們也利用不同的配位基來對此結構進行研究。第 二部分則是利用釕金屬炔類錯合物與各種C=O 與S=C 進行2+2 環化 加成反應,我們主要利用亞乙烯基同時在Cα 具有親電子性與在Cβ 具 有親核性的特性來進行反應。 第一部分利用釕金屬鹵化錯合物TpRu(PPh3)LCl, (L= HN=CPh2, PPh3)與HC≡CR, (R=Ph, COOMe, SiMe3)在甲醇下進行反應,其反應 皆會產生亞乙烯基化合物的中間體而做進一步的反應。 第二部分利用釕金屬炔類錯合物TpRu(PPh3)2(—C≡C—Ph)與 Benzyl aldehyde, Trimethylacetaldehyde, Acetone, Dithiocarbon 在二氯 甲烷下進行反應,其反應TpRu(PPh3)2(—C≡C—Ph)會先亞乙烯基化合 物的中間體而做進一步的2+2 環化加成反應。
The complex [TpRuCl(PPh3)(L)] (L=PPh3, HN=CPh2, Tp= hydrotris(pyrazolyl)borate) reacts with terminal alkynes in MeOH yield cationic vinylidene complexs [TpRu=C=CHR(PPh3)(L)+] [Cl-]. When R= HC≡CSiMe3, the vinylidene derivative react further with MeOH furnishing the corresponding methoxy-carbene complex [TpRu=C(OMe) CH3 (PPh3)+][Cl-]. The latter loses PPh3 on in solution at 80℃ forming dimethoxy-carbene complex [TpRu(=C(OMe)CH3)2)+][Cl-]. When R= HC≡CPh, the vinylidene derivative react further with MeOH furnishing the neutral vinylidene complex [TpRu(=C=CHPh)(-C≡C-Ph)(PPh3)], then loses PPh3 on in solution afford 1,4-diphenyl-1-buten-3-yne complexe [TpRu(-C(Ph)=C-C≡C-Ph)]. The latter react with H2O forming the chelate complex [TpRu(-C(CH2Ph)=CHC(=O)(Ph) ]. When R=COOMe, the vinylidene derivative react further with MeOH furnishing the corresponding methoxy-carbene complex [TpRu=C(OMe) CH2COOMe(PPh3)][Cl] then afford cyclic vinyl ether derivative, [TpRuC(OMe)=CHC(O)OMe](PPh3)]. Otherwise, The vinylidene complex [TpRu=C=CHPh(PPh3)2 +] [Cl-], react with Et3N yielding the neutral complex [TpRu(C≡CPh)(PPh3)2]. Then [TpRu(C≡CPh)(PPh3)2] react with CS2, PhC(=O)H, (CH3)3C(=O)H, (CH3)2C=O, undergo [2+2] cycloaddition reaction afford [TpRu(PPh3)2(C=C(R)XY)], (R= Ph, X=CS, Y=S), (R=Ph, X=CHPh, Y=O), (R=Ph, X=CH(CH3)3, Y=O) , (R=Ph, X=C(CH3)2, Y=O).