Solution studies of dinuclear polyamine-linked platinum-based antitumour complexes

Rasha Ruhayel, I. Zgani, Susan Berners-Price, N.P. Farrell

Research output: Contribution to journalArticlepeer-review

12 Citations (Web of Science)


The aquation profiles of two novel dinuclear polyamine-linked, platinum-based antitumour complexes [{trans-PtCl((NH3)-N-15)(2)}(2){mu-((NH2)-N-15(CH2)(6)(NH2)-N-15(CH2)(6)(NH2)-N-15)}](3+) (BBR3007, 1,1/t, t-6,6, 1) and [{trans-PtCl((NH3)-N-15)(2)}(2){mu-((NH2)-N-15(CH2)(6)(NH2)-N-15(CH2)(2)(NH2)-N-15(CH2)(6)(NH2)-N-15)}](4+) (BBR3610, 1,1/t, t-6,2,6, 1') have been probed using 2D [H-1, N-15] HSQC NMR spectroscopy. Reported herein are the rate constants for the hydrolysis of 1 and 1', as well as the acid dissociation constants of the coordinated aqua ligands in their aquated derivatives. The aquation and anation rate constants for the single step aquation model in 15 mM NaClO4 (pH 5.4) at 298 K are, for 1, k(1) = 7.2 +/- 0.1 x10(-5) s(-1), k(-1) = 0.096 +/- 0.002 M-1 s(-1) and, for 1', k(1) = 4.0 +/- 0.2 x 10(-5) s(-1), k(-1) = 1.4 +/- 0.1 M-1 s(-1). The effect of the linker backbone (Pt(tetra(m) mine vs. polyamine) was evaluated by comparison with previous data for the trinuclear complex [{trans-PtCl(NH3)(2)}(2)(mu-trans-Pt(NH3)(2){NH2(CH2)(6)NH2}(2))](4+) (1,0,1/t, t, t or BBR3464). The pK(1) for 1,0,1/t, t, t (3.44) is closest to that of 1 (3.12), while the pronounced difference for 1' (4.54), means that 1' is the least aquated of the three complexes at equilibrium. pK(a) values of 5.92 were calculated for the aquated forms of both 1 and 1', which are 0.3 pK units higher than for either 1,0,1/t, t, t, or the dinuclear 1,1/t, t. The higher pKa values for both polyamine-linked compounds may be attributed to the formation of macrochelates between the central NH2 groups and the {PtN3O} coordination sphere of the aquated species.
Original languageEnglish
Pages (from-to)4147-4154
JournalDalton Transactions: an international journal of inorganic chemistry
Publication statusPublished - 2011


Dive into the research topics of 'Solution studies of dinuclear polyamine-linked platinum-based antitumour complexes'. Together they form a unique fingerprint.

Cite this