Mass spectrometric study of dirhenium biscarboxylate:purine dinucleotide complexes

Dirhenium adducts of purine dinucleotides were identified by mass spectrometry. In consecutive studies, Re2(O2C2H3)2Cl4 · 2H2O was reacted with 2′‐deoxyguanylyl(3′→5′)‐2′‐deoxyguanosine (dGpG) and 2′‐deoxyadenylyl(3′→5′)‐2′‐deoxyguanosine (dApG) in H2O or D2O. 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.