高等学校化学学报 ›› 2001, Vol. 22 ›› Issue (S1): 100.

• 研究论文 • 上一篇    下一篇

异核四面体簇合物(η5-C5H5)(η5-RC5H4)MNiFeS(CO)5(M=Mo,W)的合成及等瓣置换反应研究——(η5-C5H5)(η5-MeO2CC5H4)MoNiFe2S(CO)10的单晶分子结构

胡青眉1, 曾广怀1, 宋礼成1, 孙杰2   

  1. 1. 南开大学化学学院化学系, 元素有机化学国家重点实验室, 天津 300371;
    2. 金属有机化学国家重点实验室, 上海 200032
  • 收稿日期:2001-07-22 出版日期:2001-12-31 发布日期:2001-12-31
  • 通讯作者: 胡青眉(1942年出生),女,教授,博士生导师,从事金属有机化学研究.
  • 基金资助:

    国家自然科学基金(批准号:29972022,29872017)资助.

Synthesis and Isolobal Displacement Reactions of Heteronuclear Tetrahedral Clusters (η5-C5H5)(η5-RC5H4)MNiFeS(CO)5(M=Mo,W)

HU Qing-Mei1, ZENG Guang-Huai1, SONG Li-Cheng1, SUN Jie2   

  1. 1. Department of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China;
    2. State Key Laboratory of Organometcdlic Chemistry, Shanghai 200032, China
  • Received:2001-07-22 Online:2001-12-31 Published:2001-12-31

摘要:

通过(η5-RC5H4)MCoFeS(CO)8(1a:M=Mo,R=H; 1b:M=Mo, R=MeO2C; 1c:M=Mo, R=Me; 1d:M=Mo,R=EtO2C; 1e:M=W, R=H)与Cp2Ni的等瓣置换反应合成了簇合物(η5-C5H5)(η5-RC5H4)MNiFeS(CO)5(2a:M=Mo, R=H; 2b:M=Mo, R=MeO2C; 2c:M=Mo, R=Me; 2d:M=Mo, R=EtO2C; 2e:M=W, R=H>.进一步通过2a,b与Co2(CO)8以及2c,d与Fe2(CO)9的等瓣置换反应,分别合成了(η5-RC5H4)MoCoFeS(CO)8(la:R=H; 1b:R=MeO2C)和(η5-C5H55-RC5H4)MoNiFe2S (CO)10(3a:R=Me; 3b:R=EtO2C).新簇合物2c-e和3a,b的结构均经元素分析、IR及1H NMR谱学表征.此外,还对我们以前合成的一个3a,b类似物(η5-C5H5)(η5-MeO2CC5H4)MoNiFe2S(CO)10(3c)成功地进行了单晶结构分析.3c属单斜晶系,Cc(#9)空间群,晶胞参数a=1.0051(3) nm,b=1.5311(5) nm,c=1.7437 nm,β=105.5(3)°, Z=4.最终一致性因子R=0.025,Rw=0.033.

关键词: 等瓣置换, MCoFeS(M=Mo, W)族合物, MNiFeS(M=Mo, W)策合物, MoNiFe2S簇合物, 合成, 单晶结构

Abstract:

Through isolobal displacement reaction of (η5-RC5H4)MCoFeS(CO)8 (1a:M=Mo, R=H; 1b:M=Mo,R=MeO2C; 1c:M=Mo, R=Me; 1d:M=Mo, R=EtO2C:1e:M=W,R=H) with Cp2Ni, a series of MNiFeS clusters have been synthesized. Further isolobal displacement reactions of 2a,b with Co2(CO)8 and 2c,d with Fe2(CO)9 produce MoFeCoS clusters (η5-RC5H4)MoCoFeS(CO)8 (1a:R H; 1b:R=MeO2C) and MoNiFe2S clusters (η5-C5H5)(η5-RC5H4)MoNiFe2S(CO)10 (3a:R=Me; 3b:R=EtO2C), respectively. New cluster complexes 2c-e and 3a,b have been characterized by elemental analysis, IR, 1H NMR spectroscopy. In addition, the crystal structure of the previously reported analog of 3a,b (η5-C5H5)(η5-MeO2CC5H4)MoNiFe2S(CO)10 (3c) has been determined by X-ray diffraction techniques. 3c belongs to monoclinic system, space group Cc(#9), cell parameters a=1.0051(3) nm, b=1,5311(5) nm, c=1.7437 nm,β=105.5(3)°, Z=4. Final agreement factors R=0.025,Rw=0.033.

Key words: Isolobal displacement, MCoFeS(M=Mo, W) clusters, MNiFeS(M=Mo, W)clusters, MoNiFezS clusters, synthesis, crystal structure

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