系列Mo-Cu(Ag,Au)-Se簇合物的95Mo和31P NMR研究

波谱学杂志 ›› 1998, Vol. 15 ›› Issue (1): 9-18.

系列Mo-Cu(Ag,Au)-Se簇合物的⁹⁵Mo和³¹P NMR研究

张千峰, 曹荣, 吴达旭, 洪茂椿, 刘汉钦

中国科学院福建物质结构研究所, 结构化学国家重点实验室, 福州 350002

收稿日期:1997-07-10 修回日期:1997-09-16 出版日期:1998-02-05 发布日期:2018-01-13
作者简介:张千峰男,31岁,硕士,工程师

⁹⁵Mo AND ³¹P NMR STUDIES ON SERIES OF Mo-Cu(Ag, Au)-Se CLUSTER COMPOUNDS

Zhang Qianfeng, Cao Rong, Wu Daxu, Hong Maochun, Liu Hanqin

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, The Chinese Academy of Sciences, Fuzhou, 350002

Received:1997-07-10 Revised:1997-09-16 Online:1998-02-05 Published:2018-01-13

摘要/Abstract

摘要： 报道了含硬币金属和四硒代钼酸盐的异金属硒簇合物的⁹⁵Mo NMR研究结果和含膦配体Mo(W)-Cu(Ag,Au)-Se配合物的³¹P NMR谱学性能。发现不同硬币金属对⁹⁵Mo核的化学屏蔽效应顺序为Au > Cu > Ag;对系列Mo-Cu-Se化合物的⁹⁵Mo NMR研究结果表明:⁹⁵Mo NMR的化学位移和线宽不仅与配位的Cu原子数目有关,而且对结构的变化特别敏感;[MoSe₄]^2-离子的相对四个方向被Cu⁺配位后,其Mo核的屏蔽基本饱和;外围配体对⁹⁵Mo NMR数据影响甚微。同时还用动态⁹⁵Mo NMR谱技术跟踪配体的取代反应和从MoCu₄到MoCu₁₀核的簇骼转变过程。此外,还讨论了这些化合物在不同构型之间,同一构型不同金属中心和不同配体基团的³¹P NMR化学位移的变化特征。

关键词: ⁹⁵Mo NMR谱, ³¹P NMR谱, 异金属硒簇合物, 四硒代钼酸盐

Abstract: This paper reports the ⁹⁵Mo and ³¹P NMR results of a series of heterometallic cluster compounds containing coinage metal and tetraselenomolybdate.The investigation results indicate that ⁹⁵Mo NMR chemical shifts and linewidths are not only related to the number of coordination of Cu atoms, but also very sensitive to structural variations.The ⁹⁵Mo NMR shielding effect is mainly caused by the coiage metal atoms in the tetraselenomolybdate system and the shielding order is Au > Cu > Ag.The saturation of Mo nucleus shielding effect from the coordination of MoSe₄ moiety by four Cu atoms and very little influence on ⁹⁵Mo nucleus from the outsphere ligands are observed. Additionally, kinetic ⁹⁵Mo NMR technique was used to monitor ligand substitution reactions and cluster skeleton transformation processes from MoCu₄ to MoCu₁₀ cores. A variety of characteristics of the ³¹P NMR chemical shifts of Mo(W)-Cu(Ag, Au)-Se compounds among different structural types are also discussed.

Key words: ⁹⁵Mo NMR, ³¹P NMR, Heteroseleometallic compounds, Tetraselenomolybdate

张千峰, 曹荣, 吴达旭, 洪茂椿, 刘汉钦. 系列Mo-Cu(Ag,Au)-Se簇合物的⁹⁵Mo和³¹P NMR研究[J]. 波谱学杂志, 1998, 15(1): 9-18.

Zhang Qianfeng, Cao Rong, Wu Daxu, Hong Maochun, Liu Hanqin. ⁹⁵Mo AND ³¹P NMR STUDIES ON SERIES OF Mo-Cu(Ag, Au)-Se CLUSTER COMPOUNDS[J]. Chinese Journal of Magnetic Resonance, 1998, 15(1): 9-18.

[1]	程增江, 杜泽涵, 董华进, 颜贤忠, 冯锐. Langendorff灌流心脏的³¹P NMR谱测定[J]. 波谱学杂志, 1996, 13(5): 411-416.
[2]	施志坚, 沈卫平, 姚远, 蒋毅. 三苯基膦和三甲基氯硅烷直接引发丙烯酸乙酯基团转移聚合的核磁共振动力学研究[J]. 波谱学杂志, 1995, 12(3): 229-236.

系列Mo-Cu(Ag,Au)-Se簇合物的⁹⁵Mo和³¹P NMR研究

⁹⁵Mo AND ³¹P NMR STUDIES ON SERIES OF Mo-Cu(Ag, Au)-Se CLUSTER COMPOUNDS

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