pH-Dependent competition between κ2N[hair space]7,O( P) macrochelation and µ-N[hair space]1,N 7 oligomer formation for (η6-arene)RuII complexes of adenosine and guanosine 5′-mono-, -di- and -tri-phosphates

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Sandra Korn and William S. Sheldrick


Abstract

The pH-dependent reaction of [Ru(η6-C6H6)(D2O) 3]2+ with adenosine and guanosine 5′-mono-, -di- and -tri-phosphates has been studied by 1H and 31P-{1H} NMR spectroscopy. Diastereomeric µ-1κN1[hair space]:[hair space]2 N6, N7 co-ordinated cyclic trimers of the type [{Ru(5′-AMP)(η6-C6H6) }3] predominate for adenosine 5′-monophosphate (5′-AMP2-) in the range pH* 3.30–9.18. An X-ray structural analysis of the RuSRuSRuS diastereomer [{Ru(5′-AMP)(η6-p-MeC6H 4Pri)}3]·7.5H2O 1b established a pronounced degree of conformational flexibility in the sugar and phosphate residues. In contrast to 5′-AMP2-, cyclic trimers cannot be observed in more strongly acid solution (pH* ⩽ 3.16) for the equilibrium system 5′-ATP–(η6-C6H6)Ru II (5′-ATP4- = adenosine 5′-triphosphate) and remain relatively minor species even at neutral or higher pH* values. As confirmed by pronounced low-field 31P-{1H} NMR shifts of up to 7.8 and 8.6 ppm for the β- and γ-phosphorus atoms, κ3N7, O(P β), O(Pγ) macrochelates provide the dominant metal species in acid solution. Time-dependent NMR studies for 5′-ADP–(η6-C6H6)Ru II (5′-ADP3- = adenosine 5′-diphosphate) indicated that initial macrochelation of this nucleotide is followed by cleavage of the β-phosphate group and formation of cyclic trimers of 5′-AMP2-. Reaction of guanosine 5′-monophosphate (5′-GMP2-) with [Ru(η6-C6H6)(D2O) 3]2+ afforded κN7-co-ordinated 1[hair space]:[hair space]1 and 2[hair space]:[hair space]1 complexes in the range pH* 3.69–8.38. In addition to analogous 1[hair space]:[hair space]1 and 2[hair space]:[hair space]1 species, κ3N7, O(Pβ), O(Pγ) macrochelates are observed for the 5′-GTP–(η6-C6H6)Ru II equilibrium system (5′-GTP4- = guanosine 5′-triphosphate) in acid solution. Initial macrochelation in the 5′-GDP–(η6-C6H6)Ru II system (5′-GDP3- = guanosine 5′-diphosphate) again leads to rapid cleavage of the terminal β-phosphate function.


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