Mass spectrometric study of dirhenium biscarboxylate:purine dinucleotide complexes

Dirhenium adducts of purine dinucleotides were identified by mass spectrometry. In consecutive studies, Re 2 (O 2 C 2 H 3 ) 2 Cl 4  · 2H 2 O was reacted with 2′‐deoxyguanylyl(3′→5′)‐2′‐deoxyguanosine (dGpG) and 2′‐deoxyadenylyl(3′→5′)‐2′‐deoxyguanosine (dApG) in H 2 O or D 2 O. These reactions were monitored to identify novel dinuclear rhenium:dinucleotide complexes as confirmed by matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOFMS), electrospray ionization mass spectrometry (ESI‐MS) and collision‐induced dissociation tandem mass spectrometry (CID MS/MS) experiments. However, the most abundant adducts detected by ES‐MS were dirhenium:nucleotide species. Of these, guanine‐containing ions were observed with highest ion counts suggesting a preference for guanine coordination. Dimetal adducts showed coordination of the purine bases and common metalated fragments were observed for both dGpG and dApG reactions. Copyright © 2007 John Wiley & Sons, Ltd.