高等学校化学学报 ›› 1991, Vol. 12 ›› Issue (1): 6.

• 论文 • 上一篇    下一篇

具有三重Mo-Mo键的配合物Mo2Cl6[SC(NH2)2]3·2H2O合成、晶体结构和电子构型

林帆, 刘世雄, 林墀昌   

  1. 中国科学院福州结构化学开放实验室, 福州大学结构化学研究室, 350002
  • 收稿日期:1989-03-25 出版日期:1991-01-24 发布日期:1991-01-24
  • 通讯作者: 刘世雄
  • 基金资助:

    国家自然科学基金

The Synthesis, Crystal Structure and Electronic Configuration of a Complex Mo2Cl6[SC(NH2)2]·2H2O with Triple Mo-Mo Bonds

Lin Fan, Liu Shi-xiong, Lin Chi-chang   

  1. Fuzhou Laboratory on Strructural Chemistry, Academia Sinica, Institute of Structural Chemistry, Fuzhou University, Fuzhou, 350002
  • Received:1989-03-25 Online:1991-01-24 Published:1991-01-24

摘要: 分别通过Mo≡Mo→Mo≡Mo的双电子氧化还原反应及由单核Mo(Ⅲ)配合物经硫脲[SC(NH2)2]桥联的方法合成具有三重Mo-Mo键的配合物Mo2Cl5[SC(NH2)2]3·2HO.该配合物晶体的结晶学参数为:三斜晶系,PI空间群,a=8. 747(1)Å, 6=9. 224(1)Å. c=13. 733(2)Å,α=103. 35(1)°, β=94. 02(1)°, γ=112. 40(1)°, V=981. 3Å3,Z=2, Dc=2. 359 g .cm-3晶胞中2个结晶学独立的分子中Mo-Mo键长分别为2.439(1)Å和2.443(1)Å.配合物的S-C键削弱了桥S原子参与d-p相互作用的程度,有利于形成较强的Mo≡Mo键,其d-d分子轨道的电子构型是ν2(π+δ)4.

关键词: 硫脲, 三重Mo-Mo键, d-p相互作用, 晶体结构, 电子构型

Abstract: The complex Mo2C16[SC(NH2)2]·2H2O was synthesized by the redox reaction of Mo≡Mo →Mo≡Mo, and by that of a mononuclear Mo(Ⅲ) complex (NH4)2MoCl3(H2O) with thiourea SC(NH2)2.The crystal of the complexis crystalized in triclinic P1 space group. The parameters of the link cell are a=8. 747(1)Å, 6=9. 224(1) Å. c=13. 733(2)Å,α=103. 35(1)°, β=94. 02(1)°, γ=112. 40(1)°, V=981. 3Å3,Z=2, Dc=2. 359 g·cm-3and the final R=0. 032, R=0. 037. for 4201 reflections with 1≥3σ(1). The coordination geometry of the two Mo(Ⅲ) atoms is a distorted octahedron Cl3MoS3,in which the three Satoms are shared between the two Mo atoms. Of the two crvstallographically independent molecules, the Mo-Mo bond lengths are 2. 439(1)Å,2. 443(1)Å respectively and the S-C distances about 0. 06Å longer than that in thiourea molecule because of the bridge coordination of Satoms and a certain d-π back bonding in the complex. The S-Cbonds weaken the d-p interactions between the Mo atoms and the Satoms, and so strengthen the Mo-Mo bonds. The electronic configuration of d-d molecular orbitals in the complex is σ2(π+ δ)4, indicated by EHMO calculation.

Key words: Thiourea, Triple Mo-Mo bond, d-p interaction, Crystal structure, Electronic configuration

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