有机化学 ›› 2006, Vol. 26 ›› Issue (03): 324-328. 上一篇    下一篇

研究论文

含硅铁键环状化合物[Me2Si-η5-C5H4Fe(CO)(PPh3)][Me2Si-η5-C5H4Fe- (CO)2-n(PPh3)n] (n=0或1)的合成与结构

孙怀林*, 黄学斌,滕向党   

  1. (南开大学化学系 天津 300071)
  • 收稿日期:2005-04-11 修回日期:2005-09-16 发布日期:2006-02-28
  • 通讯作者: 孙怀林

Synthesis and Molecular Structure of SiFe Bond-Containing Cyclic Complexes [Me2Si-η5-C5H4Fe(CO)(PPh3)][Me2Si-η5- C5H4Fe(CO)

SUN Huai-Lin*,HUANG Xue-Bin,TENG Xiang-Dang   

  1. (Department of Chemistry, Nankai University, Tianjin 300071)
  • Received:2005-04-11 Revised:2005-09-16 Published:2006-02-28
  • Contact: SUN Huai-Lin

鉴于含硅-过渡金属键化合物作为催化剂具有重要的应用价值, 在我们最近发现的化合物(η5,η5-C5H4Me2SiSi-Me2C5H4)Fe2(CO)4 (1)的硅硅键和铁铁键复分解重排反应可以有效地合成含有两个硅铁键的环状化合物[Me2Si-η5-C5H4- Fe(CO)2]2 (2)的基础上, 对该硅铁键环状化合物的三苯基膦取代衍生物[Me2Si-η5-C5H4-Fe(CO)(PPh3)][Me2Si-η5-C5H4Fe(CO)2-n(PPh3)n] (3: n=0, 5: n=1)的合成方法进行了研究. 发现化合物1在三苯基膦存在下的复分解重排反应是合成单三苯基膦取代产物3的最好方法; 而双三苯基膦取代化合物5则可通过光照条件下2与三苯基膦发生羰基取代反应而得到, 产物中含有的顺反异构体可利用制备薄层色谱法分离. 利用X射线衍射法测定了化合物3的分子结构, 考察了三苯基膦配体的存在对分子结构的影响以及三苯基膦与铁形成的配位键的稳定性.

关键词: 硅铁键, 羰基配体, 三苯基膦配体, 晶体结构

Since silicon-transition metal bond-containing compounds have important applications as catalyst, on the basis of our previous finding that the rearrangement reaction of (η5,η5-C5H4Me2SiSiMe2- C5H4)Fe2(CO)4 (1) through metathesis of Si—Si and Fe—Fe bonds provided an effective route to prepare Si—Fe bond-containing cyclic complex [Me2Si-η5-C5H4Fe(CO)2]2 (2), the syntheses of PPh3-substituted derivatives of the Si—Fe bonded cyclic structure, namely [Me2Si-η5-C5H4Fe(CO)(PPh3)][Me2Si-η5-C5H4Fe- (CO)2-n(PPh3)n] (3: n=0 and 5: n=1), were studied in the present paper. It was found that the metathetical rearrangement reaction of 1 in the presence of PPh3 was the preferred method for preparing the mono-PPh3 substituted complex 3, while the bis-PPh3 substituted prod-uct 5 might be obtained through CO substitution of 3 for PPh3 under photo-chemical conditions, and the cis and trans isomers of the product could be separated by preparative TLC. The molecular structure of 3 has been determined by the X-ray diffraction method. The influences on the molecular structure by PPh3 substitution as well as the stability of the PPh3 to Fe coordination bond were examined.

Key words: carbonyl ligand, triphenylphosphine ligand, crystal structure, Si—Fe bond