Ruthenium is a platinoid that exhibits a range of unique chemical properties in solution, which are exploited in a variety of applications, including luminescent probes, anticancer therapies, and artificial photosynthesis. This paper focuses on a recently demonstrated ability of this metal in its +3 oxidation state to form highly stable complexes with tris (hydroxymethyl)aminomethane (H
2NC(CH
2OH)
3, Tris‐base or T) and imidazole (Im) ligands, where a single Ru
III cation is coordinated by two molecules of each T and Im. High‐resolution electrospray ionization mass spectrometry (ESI MS) is used to characterize Ru
III complexes formed by placing a Ru
II complex [(NH
3)
5Ru
IICl]Cl in a Tris buffer under aerobic conditions. The most abundant ionic species in ESI MS represent mononuclear complexes containing an oxidized form of the metal, ie, [X
nRu
IIIT
2 – 2H]
+, where X could be an additional T (
n = 1) or NH
3 (
n = 0‐2). Di‐ and tri‐metal complexes also give rise to a series of abundant ions, with the highest mass ion representing a metal complex with an empirical formula Ru
3C
24O
21N
6H
66 (interpreted as
cyclo(T
2RuO)
3, a cyclic oxo‐bridged structure, where the coordination sphere of each metal is completed by two T ligands). The empirical formulae of the binuclear species are consistent with the structures representing acyclic fragments of
cyclo(T
2RuO)
3 with addition of various combinations of ammonia and dioxygen as ligands. Addition of histidine in large molar excess to this solution results in complete disassembly of poly‐nuclear complexes and gives rise to a variety of ionic species in the ESI mass spectrum with a general formula [Ru
IIIHis
kT
m (NH
3)
n ? 2H]
+, where
k = 0 to 2, m = 0 to 3, and
n = 0 to 4. Ammonia adducts are present for all observed combinations of
k and
m, except
k =
m = 2, suggesting that [His
2Ru
IIIT
2 ? 2H]
+ represents a complex with a fully completed coordination sphere. The observed cornucopia of Ru
III complexes formed in the presence of histidine is in stark contrast to the previously reported selective reactivity of imidazole, which interacts with the metal by preserving the RuT
2 core and giving rise to a single abundant ruthenium complex (represented by [Im
2Ru
IIIT
2 ? 2H]
+ in ESI mass spectra). Surprisingly, the behavior of a hexa‐histidine peptide (HHHHHH) is similar to that of a single imidazole, rather than a single histidine amino acid: The RuT
2 core is preserved, with the following ionic species observed in ESI mass spectra: [HHHHHH·(Ru
IIIT
2)
m ? (3
m‐1)H]
+ (
m = 1‐3). The remarkable selectivity of the imidazole interaction with the Ru
IIIT
2 core is rationalized using energetic considerations at the quantum mechanical level of theory.
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