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Abstract
Bifunctional neutral half-sandwich RuII complexes of the type [(η6-arene)Ru(NH3)Cl2] where arene is p-cym (1) or bip (2) were synthesised by the reaction of N,N-dimethylbenzylamine (dmba), NH4PF6 and the corresponding RuII arene dimer, and were fully characterised. X-ray crystallographic studies of [(η6-p-cym)Ru(NH3)Cl2]·{(dmba–H)(PF6)} (1a) and [(η6-bip)Ru(NH3)Cl2] (2) show extensive H-bond interactions in the solid state, mainly involving the NH3 and the Cl ligands, as well as weak aromatic stacking interactions. The half-lives for the sequential hydrolysis of 1 and 2 determined by UV/Vis spectroscopy at 310 K ranged from a few minutes for the first aquation to ca. 45 min for the second aquation; the diaqua adducts were the predominant species at equilibrium. Arene loss during the aquation of complex 2 was observed. Upon hydrolysis, both complexes readily formed mono- and di-9-ethylguanine (9-EtG) adducts in aqueous solution at 310 K. The reaction reached equilibrium after ca. 1.8 h in the case of complex 1 and was slower but more complete for complex 2 (before the onset of arene loss at ca. 2.7 h). Complexes 1 and 2 were not cytotoxic towards A2780 human ovarian cancer cells up to the maximum concentration tested (100 μM).
Highlights
Soon after the discovery of the cytotoxic properties of cisplatin,[1,2,3] extensive studies of platinum am(m)ine halido analogues led to a series of empirical rules governing the chemotherapeutic potential of this class of derivatives.[4]
The synthetic routes were rather complicated and often gave mixtures of products. They involved reacting [(η6-benzene)M(Cl)2]2 dimers in concentrated aqueous ammonia and methanol, followed by the addition of a saturated aqueous NH4PF6 solution to precipitate the complexes as the corresponding PF6 salts
The first step in the synthesis is believed to involve a fast reaction between the base N,N-dimethylbenzylamine and NH4+ to form NH3 in situ which reacts with the RuII arene dimer to afford complexes 1 and 2
Summary
Bifunctional neutral half-sandwich RuII complexes of the type [(η6-arene)Ru(NH3)Cl2] where arene is p-cym (1) or bip (2) were synthesised by the reaction of N,N-dimethylbenzylamine (dmba), NH4PF6 and the corresponding RuII arene dimer, and were fully characterised. The half-lives for the sequential hydrolysis of 1 and 2 determined by UV/Vis spectroscopy at 310 K ranged from a few minutes for the first aquation to ca. 45 min for the second aquation; the diaqua adducts were the predominant species at equilibrium. Arene loss during the aquation of complex 2 was observed. Upon hydrolysis, both complexes readily formed mono- and di-9-ethylguanine (9-EtG) adducts in aqueous solution at 310 K. 1.8 h in the case of complex 1 and was slower but more complete for complex 2 Complexes 1 and 2 were not cytotoxic towards A2780 human ovarian cancer cells up to the maximum concentration tested (100 μM)
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