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

STUDIES ON NUCLEOPHILIC SUBSTITUTION REACTION OF μ-ACYL IRON-SULFUR COMPLEXES--SYNTHESIS AND STRUCTURES OF SOME PPh_3-OR AsPh_3-SUBSTITUTED μ-ACYL Fe-S COMPLEXES

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=10.536(2),b=11.714(4),c=14.841(8)A;a=98.47(4),β=102.70(4),γ=105.78(3)°;V=1677.1A^3;Z=2;D_C=1.468g·cm^(-3).最终偏离因子R=0.065.

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 correspondingμ-acyl complexes (μ-ArCO) (μ-RS)Fe_2(CO)_6 with PPh_3 in boiling benzene for 2h orwith AsPh_3 in the same solvent refluxing for 12h. For these new substituted deriva-tives the structures were characterized by combustion analysis, IR and ~1H NMR spec-troscopy. Furthermore, the crystal structure of one representative of these new com-plexes (μ-ρ-ClC_6H_4CO) (μ-B_u^t S)Fe_2(CO)_5PPh_3 has been determined by an X-ray dif-fraction technique. The crystals belong to triclinic system with space group P1. Thecell parameters are a = 10. 536(2), b = 11.714(4), c= 14.84(8) A; a = 98.47(4), β=102.70(4), γ= 105.78(3)°; V = 1677.1 A^3; Z = 2; D_c= 1.468g·cm^(-3). Final devia-tion factor R = 0.065.