臺灣博碩士論文加值系統

以丙二酸二乙酯為起始物, 經多步合成轉換, 而得(2- 氯甲基)-3-氯丙基
苯基硫醚. 硫醚與二異丙磷基陰離子反應而得到新三腳柱型配位基: 2-
苯硫甲基-1,3-雙(二異丙磷)基丙烷 P2S. P2S可與二價鎳形成平面四方形
結構的錯合物. 此錯合物可用氰化鈉行去錯合反應重新產生配位基P2S.
磷, 硫混合供體配位基與NiCl2(DME), (CH3CN)2PdCl2 和 (CH3CN)2PtCl
反應而得(PS)MCl2, M = Ni, Pd, Pt. 這些錯合物的 syn 異構物, 可藉
由硫供體的角錐反轉而成 anti 異構物. 其轉換能障可分別計算而得. 加
入三苯基磷於 Pd, Pt 錯合物的溶液, 分別產生配位基置換的產物後, 再
於硫原子進行去烷基反應.

Starting from diethyl malonate, [(2-chloromethyl)-3-
chloropropyl] phenyl sulfide is synthesized after a series
synthetic transforma tion. This sulfide reacts with diisopropyl
phosphide to produce a new tripodal ligand:
2-phenylthiomethyl-1,3-bis(diisopropylphosph ino)propane. P2S
acts as a bidentate ligand with nickel(II) to form a square
planar complex which will be decomplexed by sodium cyanide to
regenerate free ligand. A mixed phosphorus and sulfur donor
ligand reacts with NiCl2(DME) , (CH3CN)2PdCl2, and (CH3CN)2
PtCl2 to give (PS)MCl2 ( M=Ni, Pd, Pt). The syn isomer of these
complexes readily convert into their corresponding anti isomer
which is resulted the inversion of sulfur donor center. The
inversion barriers were determined.Addi- tion of
triphenylphosphine to a solution of (PS)PtCl2, (PS)PdCl2
produces ligand substitution products cis-[(PS)Pt(PPh3)Cl]+ and
cis-[(PS)Pd(PPh3)Cl]+ respectively, which undergoes
dealkylation reaction at sulfur center to yield {P,S-[C6H4(
PPhCH2CH3)(S)]}M- (PPh3)Cl, M=Pd, Pt.