摘要
进行了系列三核羧酸配合物 [M3O(O2 CCH3) 6(THF) 3]X (M3=Cr3,X =ClO4;M3=Cr2 V ,CrV2 ,V3,X =M Cl5(M 统计为 2 /3Cr+1 /3V) ,etc)的快原子轰击质谱 (FAB MS)研究 ,在V3和Cr3两个同三核配合物中 ,V配合物易脱RCO ,而Cr配合物更易脱RCO2 。在Cr2 V和CrV2 两个异三核配合物中观察到重组反应 :Cr2 V除 [Cr2 V]还生成含有 [Cr3]重组生成的碎片离子 ,CrV2 除 [CrV2 ]则生成含有 [Cr3],[Cr2 V],[V3]等其它三种重组碎片离子。充实了前文所探讨得重组原因和规律 ,根据重组反应 ,确定了金属离子反应速率顺序为Cr >V。根据所脱落的碎片 ,初步探讨了此类三核羧酸配合物催化羧酸脱羧成酮的机理。
A series of carboxylato complexes [M3O(O2CCH3)(6)(THF)(3)]X (M-3 = Cr-3, Cr2V, CrV2, V-3; X = Cl, ClO4, VCl5, etc) are studied by the Fast Atom Bombardment Mass Spectra (FAB-MS), The RCO fragment is more easily broken off from V carboxylato than from Cr carboxylato, while RCO2 fragment is more easily broken off from Cr carboxylato. From the recombination reaction of two heterotrinuclear carboxylato complexes([1]), the reaction rate of metals is concluded as Cr > V. On the basis of some fragments of FAB-MS spectra, one possible interpretation of formation of RCOR in probe reaction is put forward.
