2017
DOI: 10.1002/slct.201701858
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Versatility of Coordination Modes in Complexes of Monohydroxamic Acids with Half‐Sandwich Type Ruthenium, Rhodium, Osmium and Iridium Cations

Abstract: Complexation of the secondary N‐methyl‐acetohydroxamic acid (HMeaha) with [(η6‐p‐cym)Ru(H2O)3]2+, [(η5‐Cp*)Rh(H2O)3]2+, [(η6‐p‐cym)Os(H2O)3]2+ or [(η5‐Cp*)Ir(H2O)3]2+ cations and the primary acetohydroxamic acid (HAha) with the former two cations (first time in the literature) has been studied in aqueous solution using pH‐potentiometry, NMR, ESI‐MS and DFT calculations. Because the arene or arenyl ligands take three coordination sites of the metal ion, only three remain free for interaction with additional lig… Show more

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Cited by 7 publications
(6 citation statements)
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“…As it is clearly seen in Table 4, identical equilibrium models were determined for the [(η 6 - p -cym)Ru(H 2 O) 3 ] 2+ –AlaAlaNHOH and [(η 5 -Cp*)Rh(H 2 O) 3 ] 2+ –AlaAlaNHOH systems. The only difference is that the stability constants are slightly higher for the complexes with the Ru-containing cation compared to Rh similarly as it was previously found with monohydroxamic acids and with aminohydroxamic acids [13,31]. Surprisingly, as Table 4 shows, apart from [MHL] 2+ , only dinuclear complexes are formed in these systems, which predominate even at 1:1 metal ion to ligand ratio (see inset in Figure 5) and at ligand excess.…”
Section: Resultssupporting
confidence: 55%
“…As it is clearly seen in Table 4, identical equilibrium models were determined for the [(η 6 - p -cym)Ru(H 2 O) 3 ] 2+ –AlaAlaNHOH and [(η 5 -Cp*)Rh(H 2 O) 3 ] 2+ –AlaAlaNHOH systems. The only difference is that the stability constants are slightly higher for the complexes with the Ru-containing cation compared to Rh similarly as it was previously found with monohydroxamic acids and with aminohydroxamic acids [13,31]. Surprisingly, as Table 4 shows, apart from [MHL] 2+ , only dinuclear complexes are formed in these systems, which predominate even at 1:1 metal ion to ligand ratio (see inset in Figure 5) and at ligand excess.…”
Section: Resultssupporting
confidence: 55%
“…Complex 5 is involved in a relatively fast initial reaction taking place The solution stability of the studied Ru(η 6 -p-cymene) complexes was conducted to reveal differences in their solution chemical properties, which may provide explanation for their significantly different biological activity. Solution speciation of numerous Ru(η 6p-cymene) complexes has already been characterized previously among others including complexes of hydroxamates [33], acetylacetonates [34,35], hydroxy-(thio)pyr(id)ones [36] with O,O-donor ligands, and 8-hydroxyquinoline derivatives [37,38] or pyridinecarboxylic acids [39] with N,O-donor set. General equilibrium processes which can take place in solution of the half-sandwich [Ru(η 6 -p-cymene)(X,Y)(Z)] complexes are shown in Scheme S1.…”
Section: Solution Chemical Properties Of β-Diketone and 8-hydroxyquinoline Complexmentioning
confidence: 99%
“…As is written in the Introduction and shown in numerous recent papers and reviews, such as references [58,60,61,77], and [97][98][99][100][101][102][103][104], among others, there is a great interest toward the development of new complexes with platinum group metals, including those with half-sandwich type organometallic cations. Predominantly, bidentate chelators have been involved to create new potential therapeutic agents with improved efficacy and selectivity.…”
Section: A Comparison Between the Metal Binding Effectivity Of The Discussed Amino/imidazole/peptide-hydroxamic Acids And Some Bidentate mentioning
confidence: 99%
“…The data, obtained for [(η 6 -p-cym)Ru(H 2 O) 3 ] 2+ and [(η 5 -Cp*)Rh(H 2 O) 3 ] 2+ complexes with some relevant (N,N), (N,O), (O,O), (S,O) donor-chelating ligands under comparable conditions to the ones used during the determination of the data in Table 1, have been used to calculate pM'1:1 values and are summarized in Table 4. As is written in the Introduction and shown in numerous recent papers and reviews, such as references [58,60,61,77], and [97][98][99][100][101][102][103][104], among others, there is a great interest toward the development of new complexes with platinum group metals, including those with half-sandwich type organometallic cations. Predominantly, bidentate chelators have been involved to create new potential therapeutic agents with improved efficacy and selectivity.…”
Section: A Comparison Between the Metal Binding Effectivity Of The Discussed Amino/imidazole/peptide-hydroxamic Acids And Some Bidentate mentioning
confidence: 99%