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STUDY ON BEHAVIOR OF POLYNUCLEAR COMPLEXES IN SOLUTION BY USE OF MULTINUCLEAR NMR

多核核磁共振研究溶液中多核配合物的行为

基本信息

批准号：
62470038
负责人：
SASAKI Yukiyoshi
金额：
$ 3.71万
依托单位：
THE UNIVERSITY OF TOKYO
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1988
资助国家：
日本
起止时间：
1988 至 1989
项目状态：
已结题

项目摘要

1. SYSTEMATIC MEASUREMENTS OF ^<183>W NMR ON AQUEOUS SOLUTIONS OF KEGGIN-TYPE HETEROPOLYTUNGSTATES HAVE BEEN CARRIED OUT, STRUCTURE DEPENDENCE OF ^<183>W CHEMICAL SHIFT AND CORRELATION BETWEEN CHEMICAL SHIFT AND THERMAL PARAMETERS BEEING TESTED. THE DATA COLLECTION FOR THIS PROJECT DOES NOT YET COMPLETE, AND IS IN PROGRESS.2. ^<31>P,^<51>V,^<77>SE ＆ ^<183>W NMR SPECTRA OD AQUEOUS SOLUTIONS CONTAINING NON-KEGGIN-TYPE POLYOXOMETALATES WITH KNOWN STRUCTURES HAVE BEEN OBSERVED IN ORDER TO INVESTIGATE THE EQUILIBRIA. THE SINGLE CRYSTALS ISOLATED FROM ABOVE-MENTIONED SOLUTION HAVE BEEN SUBJECTED TO X-RAY DIFFRACTION STUDIES AND THEIR STRUCTURES WERE DETERMINED.(1) H^+-MoO_4^<2->-SeO_3^<2-> AND H^+-VO_4^--SeO_3^<2->. CHEMICAL SPECIES IN SOLUTIONS AND STRUCTURES OF CRYSTALS OBTAINED FROM THE AQUEOUS SYSTEMS HAVE BEEN DETEMINED. IN THE FORMER SYSTEM, ^<77>Se NMR AND POTENTIOMETRY AGREED WELL WITH EACH OTHER. THE PROPOSED STRUCTURE WAS CONFIRMED BY USE OF SINGLE CRYSTAL X-RAY DIFFRACTION. THE SO … More LUTION DISSOLVING THE CRYSTAL SHOWED A ^<77>Se NMR SPECTRA CONSISTENT WITH THOSE OBSERVED IN SYSTEMATIC MEASUREMENTS ON THE AQUEOUS SYSTEM. ON THE OTHER HAND, THERE WERE NO HETROPOLYVANADATES DETECTED IN THE LATTER SYSTEM, ANDDECAVANADATE, METAVANADATE AND SELENITE IONS WERE FOUND TO BE PREDOMINANT SPECIES THROUGH THE REGION MEASURED. THE STRUCTURE OF THE CRYSTAL OBTAINED FROM THIS SYSTEM REVEALED THE HETEROPOLYVANADATE TO BE A NOVEL TYPE, AND ITS CONSTITUTION WAS NOT AGREED WITH THOSE DESCRIBED IN THE LITERATURES.(2) H^+-MoO_4^<2->-HPO_3^<2->. ^<31>P NMR OF THE SYSTEM HAS BEEN MEASURED AND THE STRUCTURE OF CRYSTAL ISOLATED FROM THIS SYSTEM WERE DETERMINED. THE HETEROPOLYANION WAS PROVED TO HAVE NON-ACIDIC PROTONS LIKE AS PHOSPHITE ION.3. FINDINGS OF NOVEL PEROXOTUNGSTATES. AMORPHOUS "CWHPA" DIRECTLY FORM THE REACTION OF TUNGSTENCARBIDE AND HYDROGEN PEROXIDE HAS BEEN REPRODUCED BY MIXTURES OF TUNGSTATE, OXALATE AND HYDROGEN PEROXIDE IN AQUEOUS SYSTEM, ^<13>C NMR, IR AND RAMAN SPECTRA BEING APPLIED. COMPARISON OF CRYSTAL STRUCTURES AND CHEMICAL SHIFTS OF NMR REVEALED DIFFERENT GEOMETRIES ABOUT C-O BONDS TO GIVE DISTINCT ^<13>C NMR CHEMICAL SHIFTS. THIS PROJECT IS ALSO UNDER FURTHER CONSTRUCTION. Less

1.本文<183>对Keggin型杂多钨酸盐水溶液进行了~ 13 W NMR谱的测定，并对~ 13 W化学位移的结构依赖性<183>和化学位移与热参数的关系进行了检验。该项目的数据收集尚未完成，正在进行中。本文用~ 1 <31>P、~ <51>1V、~ 1 <77>SE和~ 1 <183>W核磁共振谱研究了含有已知结构的非Keggin型多氧金属酸盐的水溶液的平衡。从上述溶液中分离出的单晶经X射线衍射研究，并确定了其结构。(1)H^+-MoO_4^<2->-SeO_3^<2->和H^+-VO_4^-SeO_3^<2->。测定了水溶液中的化学形态和水溶液中晶体的结构。在前一个体系中，~ 1 <77>Se NMR和电位滴定法能很好地相互配合。通过使用单晶X射线衍射证实了所提出的结构。的SO ...更多信息溶液溶解晶体的~ 13 <77>Se NMR谱与水溶液体系的化学测量结果一致。另一方面，在后一系统中没有检测到杂多钒酸盐，并且发现十钒酸盐、偏钒酸盐和亚硒酸盐离子是测量区域的优势种。从该体系中得到的晶体结构表明，杂多钒酸盐是一种新的类型，其组成与文献中描述的组成不同。(2)H^+-MoO_4^<2->-HPO_3^<2->.测定<31>了该体系的~ 1 P NMR谱，并对从该体系中分离出的晶体进行了结构分析。证明了杂多阴离子具有与亚磷酸根离子类似的非酸性质子.新型过氧钨酸盐的发现。本文报道了钨酸盐、草酸盐和过氧化氢混合物在水体系中直接生成碳化钨和过氧化氢反应生成的非晶态“CWHPA”，并应用~ 13 <13>CNMR、IR和拉曼光谱进行了研究。晶体结构和核磁共振化学位移的比较揭示了不同几何构型的碳-氧键，从而给出了不同的~ <13>1C NMR化学位移。该项目也在进一步建设中。少