Tuning the Hydrolytic Properties of Half‐Sandwich‐Type Organometallic Cations in Aqueous Solution

Abstract

Hydrolysis of half-sandwich-type platinum metal cations with the general formula [M(η 6 -arene)(H 2 O) 3 ] 2+ {M = Ru, Os; η 6 -arene = benzene, toluene, 1-methyl-4-isopropylbenzene (p-cym), or 1,3,5-triisopropylbenzene (tri-iPr)} or [Ir(η 5 -Cp*)-(H 2 O) 3 ] 2+ (Cp* = pentamethylcyclopentadienyl anion) was studied in aqueous solution in the presence of 0.20 M KNO 3 or KCl as a background electrolyte to explore the effects of the type of metal ion, the moderately coordinating monodentate chloride ion, and the electron-donating ability of the arene ligand. Replacement of Ru by Os enhances the formation of the biologically less-active, triple hydroxido-bridged dimer, [{M(η 6 -arene)} 2 (μ 2 -OH) 3 ] + , whereas in the presence of [a]

Comparative solution equilibrium and structural studies of half-sandwich ruthenium(II)(η6-toluene) complexes of picolinate derivatives

“…β(M p L q H r ) is defined for the general equilibrium: based on the pH-potentiometric titration data in the presence of chloride ions and were found to be in fairly good agreement with previously published data [44]. octanol/buffered aqueous solution at pH 7.40 at various chloride concentrations using UV-vis detection as described in our former work [24].…”

Versatility of Coordination Modes in Complexes of Monohydroxamic Acids with Half‐Sandwich Type Ruthenium, Rhodium, Osmium and Iridium Cations

“…[13,14] (iii) In the present study, our goal was also to obtain information about the effect of the change of the R N substituent from methyl (HMeaha) to hydrogen (HAha) on the complexation with the studied half-sandwich type platinum metals. (iv) Since in previous works chloride ion was found to cooordinate to these ions [12,[16][17][18][19] in order to eliminate any competition between this anion and the investigated monohydroxamate ligands the practically non-coordinating nitrate was used to maintain a constant ionic strength.…”

Complex formation between [(η6-p-cym)Ru(H2O)3]2+ and oligopeptides containing three histidyl moieties

“…According to previous studies [32,33] the functional B3P86 was used which ensures a high degree of accuracy in the prediction of the structures of transition metal complexes [34]. The relativistic small-core ECPs SDD (the Stuttgart-Dresden ECP) [35] and LANL2DZ [36] with the corresponding valence basis sets were employed on the ruthenium, and 6-311g on the ligand.…”