Unusually high oxidation states of transition metals in anhydrous phosphates (B07)

在项目B7的第一部分中，针对过渡金属的高氧化态，将合成NASICON型磷酸盐Na 3Cr 2（PO 4）3、NaCrMV（PO 4）3、NaMnIIIMV（PO 4）3和NaFeIIIMV（PO 4）3（M：Nb，Ta），并对其脱嵌行为进行表征。研究Ag 3CrIII（PO 4）2、Ag 3CrIII 3（PO 4）4和Ag 9 CrIII 3（P 2 O 7）3（PO 4）2中的磷酸根阴离子与“AgCrIII P 2 O 7”、“Ag 2 CrIII 6（P 2 O 7）2（PO 4）4”和“AgCrIII 3（PO 3）6（P 2 O 7）”的氧化偶联。在项目B7的第二部分中，除了VVOPO 4-MoVOPO 4和WVOPO 4-MoVOPO 4系统中的氧化还原平衡外，还将研究固体磷酸盐（α II-VVOPO 4，（Mo-VIO 2）2 P2 O 7，WVI 2 O3（PO 4）2，WVIOP 2 O 7）中金属基（M=O）n+的动力学控制还原及其对C-H活化的意义。

In the first part of project B7, targeting high oxidation states of the transition metals, NASICON type phosphates Na3Cr2(PO4)3, NaCrMV(PO4)3, NaMnIIIMV(PO4)3, and NaFeIIIMV(PO4)3 (M: Nb, Ta) will be syn-thesized and characterized with respect to their de-intercalation behavior. Oxidative coupling of phos-phate anions in Ag3CrIII(PO4)2, Ag3CrIII3(PO4)4, and Ag9CrIII3(P2O7)3(PO4)2 to "AgCrIIIP2O7", "Ag2CrIII6(P2O7)2(PO4)4", and "AgCrIII3(PO3)6(P2O7)" will be studied. In the second part of project B7 the kinetically controlled reduction of metalyl groups (M=O)n+ in solids phosphates (alphaII-VVOPO4, (Mo-VIO2)2P2O7, WVI2O3(PO4)2, WVIOP2O7) and its significance for C-H activation will be investigated besides redox equilibria in systems VVOPO4-MoVOPO4 and WVOPO4-MoVOPO4.