μ酰基铁硫配合物亲核取代反应的研究——若干三苯膦或三苯胂μ酰基铁硫配合物的合成及结构

μ-酰基铁硫配合物(μ-ArCO)(μ-RS)Fe_2(CO)_6和PPh_3在苯中迴流2小时, 或和AsPh_3在苯中迴流12小时可分别制得相应的单取代衍生物(μ-ArCO)(μ-RS)Fe_2(CO)_5 PPh_3(Ar=Ph, R=Et或B_u~t; Ar=p-ClC_6H_4, R=B_u~t)和(μ-ArCO)(μ-RS)Fe_2(CO)_5AsPh_3(Ar=Ph, R=Et或B_u~t).除用碳氢分析, IR和~1HNMR光谱表征了这五个新取代衍生物的结构外, 还测得一个代表物(μ-p-ClC_6H_4CO)(μ-B_u~t S)Fe_2(CO)_5 PPh_3的单晶结构. 该晶体属三斜晶系, 空间群P1. 晶胞参数a=1.0536(2), b=1.1714(4), c=1.4841(8) nm; α=98.47(4), β=102.70(4), γ=105.78(3)°; V=1.6771 nm; Z=2; D_C=1.468 g·cm~(-3). 最终偏离因子R=0.065.

Studies on Nucleophilic Substitution Reaction of μ-Acyl Iron-Sulfur Complexes——Synthesis and Structures of Some PPh3-OR AsPh3-Substituted μ-Acyl Fe-S Complexes

Mono-PPh_3- or mono-AsPh_3-substituted derivatives (μ-ArCO) (μ-RS) Fe_2(CO)_5PPh_3(Ar=Ph, R=Et or B_u~t; Ar=p-ClC_6H_4, R=B_u~t) and (μ-ArCO) (μ-RS)Fe_2(CO)_5AsPh_3 (Ar=Ph, R=Et or B_u~t) have been synthesized through reaction of the corresponding μ-acyl complexes (μ-ArCO) (μ-RS)Fe_2(CO)_6 with PPh_3 in boiling benzene for 2 h or with AsPh_3 in the same solvent refluxing for 12 h. For these new substituted derivatives the structures were characterized by combustion analysis, IR and ~1H NMR spectros. Furthermore, the crystal structure of one representative of these new complexes (μ-p-ClC_6H_4CO)(μ-B~t_uS)Fe_2(CO)_5PPh_3 has been determined by an X-ray diffraction technique. The crystals belong to triclinic system with space group P1. The cell parameters are a=1.0536(2), b=1.1714(4), c=1.4841(8) nm; α=98.47(4), β=102.70(4), γ=105.78(3)°; V=1.6771 nm; Z=2; D_C=1.468 g·cm~(-3). Final deviation factor R=0.065.