波谱学杂志 ›› 2000, Vol. 17 ›› Issue (5): 389-394.

• 研究论文 • 上一篇    下一篇

些V/S,V/Fe/S和Mn/O簇合物溶液化学行为的NMR研究

陈昌能, 朱红平, 张琰, 刘秋田, 吴达旭   

  1. 结构化学国家重点实验室中国科学院福建物质结构研究所, 福州 350002
  • 收稿日期:2000-06-16 修回日期:2000-07-07 出版日期:2000-10-05 发布日期:2018-01-11
  • 作者简介:陈昌能(1953-),男,副研究员
  • 基金资助:
    国家自然科学基金(No.29733090和29973047)资助;国家重点基础研究专项经费(G1998010100)资助

STUDY ON SOLUTION CHEMISTRY OF SOME V/S, V/Fe/S AND Mn/O CLUSTER COMPOUNDS BY NMR SPECTROSCOPY

CHEN Chang-neng, ZHU Hong-ping, ZHANG Yan-shi, LIU Qiu-tian, WU Da-xu   

  1. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, The Chinese Academy of Sciences, Fuzhou, Fujian 350002, China
  • Received:2000-06-16 Revised:2000-07-07 Online:2000-10-05 Published:2018-01-11

摘要: 报道我们对某些V/S,V/Fe/S和Mn/O簇合物溶液化学的核磁研究.
(Et4N)[V4S4(C4H8NCS2)6](1)的1H NMR谱包含三个宽峰,δ4.77,5.17和7.57,分别归属为端基与桥基配体的α-H.游离配体信号的出现表明了溶液中发生配体与溶剂分子的交换反应.
对一系列[VFe3S4(R2 NCS2)4]-簇合物(R2=OC4H8(2),Et2(3))进行了1H NMR表征.钒与三个铁中心的配体氢谱被分别归属.对NMR谱的时间跟踪发现位于δ19.6(2)以及δ34.2(3)的信号逐渐增长,这意味着新物种形成.合成反应的动态NMR跟踪指认了新物种为Fe4S4(R2 NCS2)4.提出了溶液中簇骼金属原子交换机理.
包含H2O和NO3配体的单核锰bpy配合物(4)的氢谱指示出这些单齿配体的可交换性.它促使配合物4成为含有两个单核Mn分子的包容化合物.

关键词: 核磁共振, 溶液化学, 金属簇合物

Abstract: This paper reports some interesting prollemsion solution chemistry of V/S,V/Fe/S and Mn/O cluster compounds by their NMR studies.
The 1H NMR spectrum of[V4S4(C4H8NCS2)6]- shows three broad resonances at 4.77, 5.17 and 7.57ppm which were assigned to the α-H of C4H8NCS2 ligands in terminal and bridged ligations. The signals of free C4H8NCS2 are also observed, which occur from an exchange between the R2NCS2 ligand and the solvent molecules.
The 1H NMR spectra of a series of[VFe3S4(R2NCS2)4]- were determined in DMSO-d6, exhibiting two sets of signals assigned to the α-H of the R2NCS2 ligands linking to V and Fe sites, respectively. A broad peak centered at 19.6ppm for complex 2 or at 33ppm for 3 was found to grow up with time going on, indicating the formation of Fe4S4(R2NCS2)4(R2=OC4H8,Et2). This assignment was identified by a dynamic tracing 1H NMR experiment in which Fe4S4(R2NCS2)4 was synthesized and its 1H NMR signals were monitored. A possible metal exchange accompanying the formation of Fe4S4(R2NCS2)4 in DMSO solution was suggested.
The 1H NMR spectrum of mononuclear Mn bpy complex 4 containing H2O and NO3 ligands was determined, indicating the exchangeability of these monodentate ligands, which makes 4 become an inclusion compound including two mononuclear Mn molecules.

Key words: NMR, Solution chemistry, Metallic cluster compound

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