| Summary: | 碩士 === 國立臺灣大學 === 化學學系 === 82 === 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.
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