Organometallic complexes as anion hosts

Pérez, Julio; Riera, Lucı́a

doi:10.1039/b711910k

Cited by 75 publications

(25 citation statements)

References 74 publications

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“…The enhanced solubility of the compounds relative to the free ligands is attributable to the blocking of the hydrogen-bonding acceptor atoms of the ligands (N atoms) after coordination and, in the cationic complexes, to the cation−cation repulsion, as well as the anion interposition, all of which contribute to disruption of the intermolecular hydrogen bonds that build the strong selfassociation in the crystal network of the free ligands. 27 Nevertheless, the solubility values show a strong dependence on the counterion, the overall charge of the complex (related to the formal charge of the ligands) and the arene identity. The chloride salts are much more soluble in water than their BF 4 − counterparts, in agreement with the trend observed in the literature for other families of ruthenium(II) arene complexes, which is explained as a result of the high hydration energy attributed to the Cl − anion.…”

Section: ■ Introductionmentioning

confidence: 99%

Derivation of Structure–Activity Relationships from the Anticancer Properties of Ruthenium(II) Arene Complexes with 2-Aryldiazole Ligands

et al. 2014

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The ligands 2-pyridin-2-yl-1H-benzimidazole (HL(1)), 1-methyl-2-pyridin-2-ylbenzimidazole (HL(2)), and 2-(1H-imidazol-2-yl)pyridine (HL(3)) and the proligand 2-phenyl-1H-benzimidazole (HL(4)) have been used to prepare five different types of new ruthenium(II) arene compounds: (i) monocationic complexes with the general formula [(η(6)-arene)RuCl(κ(2)-N,N-HL)]Y [HL = HL(1), HL(2), or HL(3); Y = Cl or BF4; arene = 2-phenoxyethanol (phoxet), benzene (bz), or p-cymene (p-cym)]; (ii) dicationic aqua complexes of the formula [(η(6)-arene)Ru(OH2)(κ(2)-N,N-HL(1))](Y)2 (Y = Cl or TfO; arene = phoxet, bz, or p-cym); (iii) the nucleobase derivative [(η(6)-arene)Ru(9-MeG)(κ(2)-N,N-HL(1))](PF6)2 (9-MeG = 9-methylguanine); (iv) neutral complexes consistent with the formulation [(η(6)-arene)RuCl(κ(2)-N,N-L(1))] (arene = bz or p-cym); (v) the neutral cyclometalated complex [(η(6)-p-cym)RuCl(κ(2)-N,C-L(4))]. The cytototoxic activity of the new ruthenium(II) arene compounds has been evaluated in several cell lines (MCR-5, MCF-7, A2780, and A2780cis) in order to establish structure-activity relationships. Three of the compounds with the general formula [(η(6)-arene)RuCl(κ(2)-N,N-HL(1))]Cl differing in the arene moiety have been studied in depth in terms of thermodynamic dissociation constants, aquation kinetic constants, and DNA binding measurements. The biologically most active compound is the p-cym derivative, which strongly destabilizes the DNA double helix, whereas those with bz and phoxet have only a small effect on the stability of the DNA double helix. Moreover, the inhibitory activity of several compounds toward CDK1 has also been evaluated. The DNA binding ability of some of the studied compounds and their CDK1 inhibitory effect suggest a multitarget mechanism for their biological activity.

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Section: ■ Introductionmentioning

confidence: 99%

Derivation of Structure–Activity Relationships from the Anticancer Properties of Ruthenium(II) Arene Complexes with 2-Aryldiazole Ligands

et al. 2014

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“…The {Mo(η 3 ‐allyl)(CO) 2 } metal fragments were selected because previous studies have shown that [Mo(η 3 ‐allyl)(CO) 2 L 3 ][BAr′ 4 ] derivatives, where L 3 represents three monodentate ligands or a tridentate ligand that occupies three fac ‐capping positions, could be straightforwardly prepared and are relatively stable 7. Tetraarylborate BAr′ 4 (Ar′=3,5‐bis(trifluoromethyl)phenyl) was chosen as the counteranion of the cationic complex hosts to minimize the competition with the anionic guests 5e,f…”

Section: Introductionmentioning

confidence: 99%

Interaction between Anions and Molybdenum Allyl Dicarbonyl Complexes of 1,4,7‐Trithiacyclononane

Morales

Puerto

Rı́o

et al. 2012

Chemistry A European J

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The labile complex [MoCl(η3‐methallyl)(CO)2(NCMe)2] reacts with the ligand 1,4,7‐trithiacyclononane ([9]aneS3) and the salt NaBAr′4 to afford [Mo(η3‐methallyl)(CO)2([9]aneS3)][BAr′4] (1⋅BAr′4). An analogous reaction of [MoBr(η3‐allyl)(CO)2(NCMe)2] yields [Mo(η3‐allyl)(CO)2([9]aneS3)][BAr′4] (2⋅BAr′4). The new compounds 1⋅BAr′4 and 2⋅BAr′4 were characterized by IR and NMR spectroscopic analysis and X‐ray diffraction studies. Both compounds feature the cyclic thioether [9]aneS3 coordinated as a tridentate ligand to the molybdenum center. The allyl ligand in 2⋅BAr′4 is aligned with the middle of the OC‐Mo‐CO angle, which is acute. Both of these features are typical of most pseudo‐octahedral allyl dicarbonyl molybdenum complexes. In contrast, the allyl group is rotated in 1⋅BAr′4, which is attributed to steric hindrance between the methyl substituent and the ligated thioether, and the OC‐Mo‐CO angle is obtuse. Compound 1⋅BAr′4 undergoes rapid substitution of [9]aneS3 by either chloride and fluoride ions in dichloromethane, and the products include the known species [{Mo(η3‐methallyl)(CO)2}2(μ‐Cl)3]− and a structurally similar new anionic complex with two fluoro and one hydroxo bridging ligands, respectively. Stable supramolecular adducts were formed in the reactions of 1⋅BAr′4 and 2⋅BAr4 with bromide, iodide, hydrogensulfate, and methanesulfonate compounds. The binding constants of these adducts in dichloromethane were calculated from 1H NMR spectroscopic titration data, and the solid‐state structures of the 1⋅Br, 1⋅HSO4, 1⋅I, and 2⋅I adducts were determined by X‐ray diffraction studies. The surprising slightly higher stability of the iodide adduct relative to that of bromide was investigated theoretically, with the results pointing to an effect of the differential solvation of the halide ions.

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“…[31][32][33] One family of metal complexes that has shown considerable promise in the design of emissive sensors has been that of the fac-rhenium(I) tricarbonyl diimine fragment, where the sixth coordination site can accommodate either a neutral ligand to give a monovalent cation, or a halide to provide a neutral complex. Anion recognition has been observed in a variety of complexes, [34][35][36][37][38][39][40] and previously we have…”

Section: Introductionmentioning

confidence: 99%

New insights into dihydrogenphosphate recognition with dirhenium(i) tricarbonyl complexes bridged by a thiourea moiety

2014

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Organometallic complexes as anion hosts

Abstract: New anion hosts have been accessed using cationic organometallic fragments with sufficient kinetic stability as geometry-organizing cores, simple ditopic ligands featuring hydrogen bond donor groups, and the inert, low interacting, lipophilic BAr9 4 anion.

Cited by 75 publications

References 74 publications

Derivation of Structure–Activity Relationships from the Anticancer Properties of Ruthenium(II) Arene Complexes with 2-Aryldiazole Ligands

Derivation of Structure–Activity Relationships from the Anticancer Properties of Ruthenium(II) Arene Complexes with 2-Aryldiazole Ligands

Interaction between Anions and Molybdenum Allyl Dicarbonyl Complexes of 1,4,7‐Trithiacyclononane

New insights into dihydrogenphosphate recognition with dirhenium(i) tricarbonyl complexes bridged by a thiourea moiety

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