系列同三核铬、锰、铁羧酸配合物的FAB-MS研究

FABMS Study on a Series of Trinuclear Carboxylato\=Complexes of Cr, Mn and Fe

进行了系列同三核羧酸配合物〔Ｍ３Ｏ（Ｏ２ＣＲ）６Ｐｙ３〕Ｘ（Ｍ＝Ｃｒ，Ｍｎ，Ｆｅ；Ｒ＝ＣＨ３，Ｃ２Ｈ５，Ｃ６Ｈ５；Ｘ＝Ｃｌ－，ＣｌＯ４－；Ｐｙ为吡啶）的快原子轰击质谱（ＦＡＢ－ＭＳ）研究。获得了包括配位吡啶在内的完整阳离子峰。在研究其断裂规律时，主要观察到４个系列碎片离子：Ⅰ．〔Ｍ３Ｏ（Ｏ２ＣＲ）ｎ〕＋，ｎ＝６～２；Ⅱ．〔Ｍ３Ｏ（Ｏ２ＣＲ）ｎＯ〕＋，ｎ＝５～１；Ⅲ．〔Ｍ２Ｏ（Ｏ２ＣＲ）ｎ〕＋，ｎ＝３～１；Ⅳ．〔Ｍ２（Ｏ２ＣＲ）ｎ〕＋，ｎ＝４～２。通过对该系列配合物质谱断裂过程的比较和分析，获得了配合物稳定性随金属离子及配体的变化如下：金属离子，Ｃｒ＞Ｍｎ＞Ｆｅ；桥配基，－ＣＨ３ＣＯ２＞－Ｃ２Ｈ５ＣＯ２＞－Ｃ６Ｈ５ＣＯ２；端配基，Ｐｙ＞Ｈ２Ｏ。本研究及先前的工作〔１，８〕还为某些三核铬，铁羧酸配合物在以乙炔加水或加氢为探针反应中存在活性物种：〔Ｃｒ３Ｏ（Ｏ２ＣＲ）３～４〕。

A series of trinuclear carboxylato complexes M3O(O2CR)6Py3X (M=Cr, Mn, Fe; R=CH3, C2H5; X=Cl-, ClO4-; Py=pyridine) are studied by the Fast Atom Bombardment Mass Spectra (FABMS), and the results are reported in this paper. Five series of the fragmentation ions M3O(O2CR)n+(n=6￣2), M3O(O2CR)nO+ (n=5￣1), M2O(O2CR)n+(n=3￣1), M2(O2CR)n+(n=4￣2), M3O(O2CR)nNBA-1+(n=5￣3)(NBA=mnitrobenzyl alcohol) have been identified mainly from their mass spectra. On the basis of the study of fragmentation regularity some useful investigation on the structural chemistry and stability of the complexes are carried out.\;