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Coordination of RuCl3(NO)(H2O)2 by imidazole, histidine and iminodiacetate ligands: a study of complexation of 'Caged NO' by simple bio-cellular donors

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Abstract

The 'caged NO' reagent, RuCl3NO(H2O)2, has been studied by n.m.r. and i.r. methods with imidazole, histidine, histamine, and N-methyliminodiacetate as complexing ligands. These ligands are representative of cellular donors that would be encountered as RuCl3NO(H2O)2 migrates through biological cells. [RuCl3NO(imH)(H2O)], [RuCl3(NO)(imH)2] and [RuCl2(NO)(imH)3]+ complexes (imH = imidazole) have been detected by 1H-n.m.r. and i.r. and electrospray mass spectrometry (e.s.i.–m.s.) methods. Based upon the effect of cis ligand addition on the ν(NO) frequency causing a decrease in frequency, the 1:1 and 1:2 complexes have the imidazole donors in the plane cis to the NO+ moiety, whereas the 1:3 species has the third imidazole trans to the NO+. The trans imidazole donor causes 'trans-strengthening' of the N–O bond of the {RuNO}6 chromophore. 1H-n.m.r. shows that the monodentate imidazole donor(s) is (are) in rapid exchange with free imidazole in solution for each of the n = 1–3 species. Histidine and histamine make kinetically more stable 1:1 complexes with the major isomer having an axially-coordinated histidine imidazole donor, but in-plane donation for histamine. The carboxylate of coordinated histidine remains pendant according to i.r. and 13C-n.m.r. data. From syntheses carried out at pH ca. 5, the amino donor is H-bonded to an in-plane H2O in the major species (ca. 75%) and coordinated with displacement of the in-plane H2O in the lesser isomer (25%). By contrast, the histamine ligand binds with an in-plane bound imidazole and a pendant protonated amino group (94%). The remaining 6% has an in-plane chelated histamine, analogous to the bis imidazole species and the known fac, cis-[RuCl3NO(en)] complex. N-Methyliminodiacetate is observed to form one main [RuCl(NO)(mida)(H2O)] complex (85%) with two chelated glycinato donor groups with RuCl3NO(H2O)2, one glycinato group chelated 'in-plane' with the central amine donor and one axial coordinated glycinato donor. A second [RuCl(NO)(mida)(H2O)] complex (the remaining 15%) has the amine donor trans to NO+ and chelated glycinato groups which coordinate in the RuClO2(OH2) plane, either cis or trans to each other, in a 60:40 split (ca. 9% and 6%). The presence of one Cl− and one H2O in the [RuCl(NO)(mida)(H2O)] complexes was established by e.s.i.–m.s. These results show that RuCl3NO(H2O)2 is likely to be freely mobile within a cellular environment, forming stable complexes via bidentate chelation with 'two-point' nitrogen donors (en, his, etc).

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  1. Department of Chemistry, University of Pittsburgh, Pittsburgh, PA, 15260, USA

    Joseph M. Slocik, Matthew S. Ward, Kasi V. Somayajula & Rex E. Shepherd

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Slocik, J.M., Ward, M.S., Somayajula, K.V. et al. Coordination of RuCl3(NO)(H2O)2 by imidazole, histidine and iminodiacetate ligands: a study of complexation of 'Caged NO' by simple bio-cellular donors. Transition Metal Chemistry 26, 351–364 (2001). https://doi.org/10.1023/A:1007194314107

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