ルテニウム（ＩＩ）多核金属錯体のＥＳＩ‐ＭＳ

Abstract

A number of polynuclear ruthenium(II), rhodium(III), and cobalt(III) bipyridine complexes have been examined by electrospray ionization mass spectrometry (ESI-MS). ESI-MS is shown to be a powerful tool for the identification of polymetallic complexes and for detecting the contamination, because ESI mass spectra for the complexes showed a simple enough mass pattern for easy structural assignment. Multiply charged ions with the charge state from 8+ to 3+ were observed in the full scan ESI mass spectra of star-burst type tetranuclear complexes denoted by [Met(II)(bpy)2B]3RuX8 (Met=Ru, Os, and bpy=2,2′-bipyridine, B=bridging ligands, X=ClO4-). Different charged ions were found to be generated by the combination of counterion loss and protonation/deprotonation at the proton site of the bridging ligand B. These ion intensities are qualitatively explained in terms of acidity of metal complexes depending upon bridging ligand structures and the charge of metal ions. Ions produced by a removal of ligands were not observed in the ESI spectra unlike the FAB spectra. For tetranuclear complexes, collision-induced dissociation (CID) of the multiply charged ions has made it clear that loss of one or more HX neutral is a major process for lower charge states, while complete fragmentation takes place for higher charge states and the fragments are based on a subunit group of [Met(II)(bpy)2B]2+. Insertion of formal O2- produced from ClO4- counterion was observed for the complexes without active protons even if low energy CID experiments, but not for the complexes with active protons. Advantages of ESI mass spectrometry are demonstrated for these polynuclear compounds and CID chemistry of the investigated ions will be discussed.