The mass spectra of some (polypyridyl)ruthenium(Il) complexes of the type [Ru,L(bpy),](PF,), (L = 2,2':6,2"-terpyridine ( x = I ), 3,3':5,3"-bis(dimethylene)-2,2':6,2"-terpyridine ( x = l), 5,6,9,10,1 l,12,l5,16-octahydrocycloota[ 1",2":5,6;4",3":5',6']dipyrido[2,3-b:2',3'-b]di[ 1 ,IO]phenanthroline ( x = 1, 2), and N,N'-dimethylene-2,2'-biimidazole ( x = I; bpy = 2,2'-bipyridine) have been investigated by using fast atom bombardment tandem mass spectrometry. The low-energy collision-induced dissociation (CID) spcctra provide confirmation of the structures and details about fragmentations of the complexes. The observed decomposition pathways involve losses of intact ligands, PF; counterions, simple bond cleavages, fluoride transfers from the PF; counterion to thc Ru(1l) center with loss of PF5, and reductive eliminations of HF. The fluoride-transfer reaction can be used to determine thc coordination of the chelating ligands in the parent complex. IntroductionR u t h e n i u m complexes containing 2,2'-bipyridine (bpy) ligands and related analogues have been the subject of recent investigations.'-3 These compounds have promise for the conversion of solar power into electrical and chemical en erg^.^-^ A variety of ruthenium complexes with ligands consisting of polyaza cavityshaped macrocycles have been synthesized with the intent of inducing unusual metal complex chemistry and optimizing photocatalytic efficien~y.~-'~ Various analyses of Ru( 11) complexes with plypyridine ligands have been reported. Others have investigated the resonance Raman spectra of various reduction products of tris(bipyridy1)-r u t h e n i u m ( l I ) . l 4 Mass spectrometric techniques for t h e characterization of involatile, intractable organometallic complexes have been successfully developed, such as field desorption (FD) mass s p e c t r~m e t r y , l~-~~ electrohydrodynamic mass spectrometry ( E H MS),'* laser desorption mass spectrometry (LDMS),I9 secondary ion mass spectrometry (SIMS),20y21 and fast atom bomb a r d m e n t ( F A B ) mass ~p e c t r o m e t r y . I~.~~-~~ In general, singly charged ions are produced by using these techniques. However, t h e observation of doubly charged ions from coordination compounds containing multiply charged cationic metal centers has been reported. Cook and co-workers have reported forming [ R u ( bpy)J2+ and [ Fe(bpy),]*+ using electrohydrodynamic mass s p e c t r o m e t r y ( E H M S ) . 1 8 Doubly charged ions, including [Ru-( bpy),12+, from coordination compounds have also been observed in FAB mass ~p e c t r a .~~?~~ In addition, t h e mass spectra of coordination complexes have been compared with their properties in ~o l u t i o n . '~~'~ The FAB process can be an energetic ionization
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