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系列Mo-Cu(Ag,Au)-Se簇合物的95Mo和31PNMR研究(英文)

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

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【作者】 张千峰曹荣吴达旭洪茂椿刘汉钦

【Author】 Zhang Qianfeng,\ Cao Rong,\ Wu Daxu, Hong Maochun * and\ Liu Hanqin (State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, The Chinese Academy of Sciences, Fuzhou, 350002)

【机构】 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

【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95MoNMR研究结果和含膦配体Mo(W)-Cu(Ag,Au)-Se配合物的31PNMR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95MoNMR研究结果表明:95MoNMR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95MoNMR数据影响甚微。同时还用动态95MoNMR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31PNMR化学位移的变化特征。

【Abstract】 This paper reports the\ 95 Mo and\ 31 P NMR results of a series of heterometallic cluster compounds containing coinage metal and tetraselenomolybdate. The investigation results indicate that\ 95 Mo 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\ 95 Mo 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 MoSe 4 moiety by four Cu atoms and very little influence on\ 95 Mo nucleus from the outsphere ligands are observed. Additionally, kinetic\ 95 Mo NMR technique was used to monitor ligand substitution reactions and cluster skeleton transformation processes from MoCu 4 to MoCu 10 cores. A variety of characteristics of the\ 31 P NMR chemical shifts of Mo(W)-Cu(Ag,Au)-Se compounds among different structural types are also discussed.

  • 【文献出处】 波谱学杂志 ,CHINESE JOURNAL OF MAGNETIC RESONANCE , 编辑部邮箱 ,1998年01期
  • 【分类号】O482.532,O635
  • 【下载频次】49
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