Can radical cations of the constituents of nucleic acids be formed in the gas phase using ternary transition metal complexes?

Electrospray ionization (ESI) tandem mass spectrometry (MS/MS) of ternary transition metal complexes of [M(L3)(N)]2+ (where M = copper(II) or platinum(II); L3 = diethylenetriamine (dien) or 2,2′:6′,2″‐terpyridine (tpy); N = the nucleobases: adenine, guanine, thymine and cytosine; the nucleosides: 2′deoxyadenosine, 2′deoxyguanosine, 2′deoxythymine, 2′deoxycytidine; the nucleotides: 2′deoxyadenosine 5′‐monophosphate, 2′deoxyguanosine 5′‐monophosphate, 2′deoxythymine 5′‐monophosphate, 2′deoxycytidine 5′‐monophosphate) was examined as a means of forming radical cations of the constituents of nucleic acids in the gas phase. In general, sufficient quantities of the ternary complexes [M(L3)(N)]2+ could be formed for MS/MS studies by subjecting methanolic solutions of mixtures of a metal salt [M(L3)X2] (where M = Cu(II) or Pt(II); L3 = dien or tpy; X = Cl or NO3) and N to ESI. The only exceptions were thymine and its derivatives, which failed to form sufficient abundances of [M(L3)(N)]2+ ions when: (a) M = Pt(II) and L3 = dien or tpy; (b) M = Cu(II) and L3 = dien. In some instances higher oligomeric complexes were formed; e.g., [Pt(tpy)(dG)n]2+ (n = 1–13). Each of the ternary complexes [M(L3)(N)]2+ was mass‐selected and then subjected to collision‐induced dissociation (CID) in a quadrupole ion trap. The types of fragmentation reactions observed for these complexes depend on the nature of all three components (metal, auxiliary ligand and nucleic acid constituent) and can be classified into: (i) a redox reaction which results in the formation of the radical cation of the nucleic acid constituent, N+.; (ii) loss of the nucleic acid constituent in its protonated form; and (iii) fragmentation of the nucleic acid constituent. Only the copper complexes yielded radical cations of the nucleic acid constituent, with [Cu(tpy)(N)]2+ being the preferred complex due to suppression, in this case, of the loss of the nucleobase in its protonated form. The yields of the radical cations of the nucleobases from the copper complexes follow the order of their ionization potentials (IPs): G (lowest IP) > A > C > T (highest IP). Sufficient yields of the radical cations of each of the nucleobases allowed their CID reactions (in MS3 experiments) to be compared to their even‐electron counterparts. Copyright © 2005 John Wiley & Sons, Ltd.