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

1.对Keggin杂多酸盐的水溶液进行了~&lt；183&gt；W核磁共振谱的系统测量，检验了~&lt；183&gt；W化学位移的结构依赖性以及化学位移与热参数的相关性。该项目的数据收集尚未完成，正在进行中。为了研究平衡，观察了含有已知结构的非Keggin-型聚氧杂多酸盐类水溶液的核磁共振波谱。对从上述溶液中分离得到的单晶进行了X射线衍射研究，确定了它们的结构：(1)H^+-MoO_4^&lt；2--gt；-SeO_3^&lt；2-&gt；和H^+-VO_4^--SeO_3^&lt；2-&gt；测定了溶液中的化学物种和从水体系中得到的晶体结构。在前一种体系中，~(77)Se-Se核磁共振与电位法吻合较好。用单晶X-射线衍射仪对所提出的结构进行了确认。The So…更多的溶液溶解该晶体，显示A^&lt；77&gt；Se核磁共振谱与在水体系中观察到的系统测量结果一致。另一方面，在后一种体系中没有检测到杂多钒酸盐，在整个测定区内发现了钙钒酸根离子、偏钒酸根离子和亚硒酸根离子。从该体系得到的晶体结构表明，杂多钒酸盐是一种新的类型，其组成与文献中所描述的不一致。(2)H^+-MoO_4^&lt；2-&gt；-HPO_3^&lt；2-&gt；测定了该体系的核磁共振谱，确定了从该体系中分离出的晶体的结构。杂多酸被证明具有类似亚磷酸根离子的非酸性质子。新的尖晶石属的发现。用钨酸盐、草酸盐和过氧化氢的混合物在水体系中直接生成无定形的“CWHPA”，用核磁共振、红外光谱和拉曼光谱进行了研究。对核磁共振的晶体结构和化学位移进行了比较，发现C-O键的几何构型不同，从而产生了不同的核磁共振化学位移。该项目也在进一步建设中。较少

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