| Summary: | 碩士 === 國立臺灣師範大學 === 化學系 === 100 === A tripodal tetradentate ligand, tris(3-(trimethylsilyl)-2- mercaptophenyl)phosphine (P(STMS)3H3) was prepared to synthesize several iron complexes. Addition of deprotonated P(STMS)33- to an acetonitrile solution of the mixture of equamolar iron tetrafluoroborate and PPN(BF4) gave an FeII complex, [PPN][Fe(CH3CN)P(STMS)3] (1). Complex 1 possesses a FeII center, coordinated by an apical phosphine, three equatorial thiolates and one acetonitrile, forming a trigonal bipyramidal geometry (τ = 0.97). Reaction of FeCl3, PPNCl and deprotonated P(STMS)33- provided an FeIII complex, [PPN][FeClP(STMS)3] (2). The bound acetoitrile of complex 1 is readily repleaced by an exogenous ligand. For instance, a purple complex [PPN][Fe(CO)P(STMS)3] (3) and a brown complex [PPN][Fe(N3)P(STMS)3] (4) were prepared from the reaction of complex 1 with CO and PPNN3, respectively. Complexes 1 – 4 were characterized by IR and UV/vis spectroscopies, and X-ray crystallography. As complex 1 reacted with dioxygen, a dark-purple species was formed, which was monitored by UV/vis spectroscopy at -80°C. The spectrum of the dark-purple species exhibited three charge transfer bands at 497, 561 and 659 nm (ε = 2205, 2284 and 2807 cm-1M-1), which were consistent with iron-oxygen species.
|
|---|
