Unravelling the versatile metal binding modes of adenine: Looking at the molecular recognition patterns of deaza- and aza-adenines in mixed ligand metal complexes

Domínguez‐Martín, Alicia; Brandi-Blanco, María del Pilar; Matilla, Ángel J.; Bakkali, Hanan El; Nurchi, Valeria Marina; González‐Pérez, Josefa María; Castiñeiras, Alfonso; Niclós‐Gutiérrez, Juan

doi:10.1016/j.ccr.2013.03.029

Cited by 38 publications

(27 citation statements)

References 117 publications

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“…This class of heterocycles has received significant attention because of the biological activity of certain derivatives, and the structural relationship between azaindoles and the purine bases found in nucleic acids. 1-7 Despite this interest, only a limited body of work has investigated the coordination chemistry of these molecules with transition metals.…”

Section: Introductionmentioning

confidence: 99%

Homoleptic Transition Metal Complexes of the 7-Azaindolide Ligand Featuring κ¹-N1 Coordination

et al. 2015

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Homoleptic complexes of the anion of 7-azaindole (AzaIn) have been synthesized and characterized for a series of 3d transition metals. For Mn(II), Fe(II), and Co(II), complexes of formula Na2[M(AzaIn)4]·2L (L = THF, 2-MeTHF, toluene, or benzene) have been isolated by treatment of the corresponding metal chloride salts with 7-azaindole in the presence of sodium hexamethyldisilazide. The complexes adopt tetrahedral geometries with exclusive coordination to the transition metal ion through the pyrrolic N1 nitrogen atoms of the AzaIn ligands. Solid-state structures of the complexes demonstrate that the sodium cations remain tightly associated to the coordination entities through interaction with both the pyrrolic and pyridine nitrogen atoms of the azaindolide ligands. For Fe(II), replacement of the sodium cations by other alkali metal ions (Li or K) generates new complexes that demonstrate similar coordination geometries to the sodium salts. As a means of comparison, the Fe(II) complex of 4-azaindolide was also investigated. Na2[Fe(4-AzaIn)4]·2L adopts a similar solution structure to the 7-azaindolide complexes as judged by NMR spectroscopy and cyclic voltammetry. DFT calculations have been performed to investigate the bonding in the 7-azaindolide complexes. Results demonstrate that 7-azaindolide-κ1-N1 is a nearly pure sigma donor ligand that features a high degree of ionic character in its bonding to mid 3d transition metal ions.

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Section: Introductionmentioning

confidence: 99%

Homoleptic Transition Metal Complexes of the 7-Azaindolide Ligand Featuring κ¹-N1 Coordination

et al. 2015

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“…They both exhibit an asymmetrically elongated octahedral coordination, type 4+1+1, although with some differences. In the environment of the Cu1 ion the Cu1-S1(thioether) bond is ( only limited structural information on neutral Hdap and its metal complexes is available [22].…”

Section: Resultsmentioning

confidence: 99%

Molecular recognition between adenine or 2,6-diaminopurine and copper(II) chelates with N,O2,S-tripodal tetradentate chelators having thioether or disulfide donor groups

González‐Pérez

Choquesillo-Lazarte

Domínguez‐Martín

et al. 2015

Journal of Inorganic Biochemistry

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“…The dissociation energy (E dis ) of each H-bond based on V r and G r parameters are also indicated in kcal/mol. In a rather comprehensive review [51] we have look at the molecular recognition patterns between metal complexes and adenine or a variety of deaza-and aza-adenines (such as Hdap) on the basis of the cooperation between coordination bonds and intra-molecular interligand H-bonding interactions. This review emphasizes the relevance of the N(heterocyclic)-H tautomeric possibilities in neutral and protonated forms of such kinds of natural or synthetic closely related N-heterocyclic ligands.…”

Section: Structural Insides On N(heterocyclic)-proton Affinities H-tmentioning

confidence: 99%

“…It is generally assumed that the proton affinity of hardly versatile ligand adenine (Hade) follows the order N9>N1>N7>N3>>N6(exocyclic amino) [51]. In a private communication to the CSD basis [55] the structure of the salt H 3 (N1,N7,N9)dapCl 2 ·H 2 O (see reference code NULCOO in CSD Database) revealed the lesser proton affinity of the N3 atom of Hdap.…”

Section: Cp#mentioning

confidence: 99%

Anion–Cation Recognition Pattern, Thermal Stability and DFT-Calculations in the Crystal Structure of H2dap[Cd(HEDTA)(H2O)] Salt (H2dap = H2(N3,N7)-2,6-Diaminopurinium Cation)

et al. 2020

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The proton transfer between equimolar amounts of [Cd(H 2 EDTA)(H 2 O)] and 2,6-diaminopurine (Hdap) yielded crystals of the out-of-sphere metal complex H 2 (N3,N7)dap [Cd(HEDTA)(H 2 O)]·H 2 O (1) that was studied by single-crystal X-ray diffraction, thermogravimetry, FT-IR spectroscopy, density functional theory (DFT) and quantum theory of "atoms-in-molecules" (QTAIM) methods. The crystal was mainly dominated by H-bonds, favored by the observed tautomer of the 2,6-diaminopurinium(1+) cation. Each chelate anion was H-bonded to three neighboring cations; two of them were also connected by a symmetry-related anti-parallel π,π-staking interaction. Our results are in clear contrast with that previously reported for H 2 (N1,N9)ade [Cu(HEDTA) (H 2 O)]·2H 2 O (EGOWIG in Cambridge Structural Database (CSD), Hade = adenine), in which H-bonds and π,π-stacking played relevant roles in the anion-cation interaction and the recognition between two pairs of ions, respectively. Factors contributing in such remarkable differences are discussed on the basis of the additional presence of the exocyclic 2-amino group in 2,6-diaminopurinium(1+) ion. Crystals 2020, 10, 304 2 of 15 reported analog of adenine, [Cu(HEDTA)(H 2 O)]·2H 2 O [5,32], was also performed. The H-bonding networks that are established at both faces of H 2 dap were also studied using DFT calculations and the relative strength of each H-bond was estimated using the QTAIM theory. The antiparallel π,π-stacking interactions that were formed between the cations were also studied, focusing on the effect of the counter-ions. Materials and Methods ReagentsH 4 EDTA acid (TCI), Hdap (Alfa Aesar) and CdCO 3 (Alfa Aesar) were used as received. CrystallographyA colorless needle crystal of H 2 dap[Cd(HEDTA)(H 2 O)]·H 2 O (1) was mounted on a glass fiber and used for data collection. Crystal data were collected at 100(2) K, using a Bruker D8 VENTURE PHOTON III-14 diffractometer. Graphite-monochromated MoK(α) radiation (λ = 0.71073 Å) was used throughout. The data were processed with APEX2 [33] and corrected for absorption using SADABS (transmissions factors: 1.000-0.962) [34]. The structure was solved by direct methods using the program SHELXS-2013 [35] and refined by full-matrix least-squares techniques against F 2 using SHELXL-2013 [35]. Positional and anisotropic atomic displacement parameters were refined for all non-hydrogen atoms. Hydrogen atoms were located in difference maps and included as fixed contributions riding on attached atoms with isotropic thermal parameters 1.2/1.5 times those of their carrier atoms. Criteria of a satisfactory complete analysis were the ratios of 'rms' shift to standard deviation less than 0.001 and no significant features in final difference maps. Atomic scattering factors were taken from the International Tables for Crystallography [36]. Molecular graphics were plotted with PLATON [37]. A summary of the crystal data, experimental details and refinement results are listed in Table 1. Crystallographic data for 1 has been deposited in the Cambridg...

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Unravelling the versatile metal binding modes of adenine: Looking at the molecular recognition patterns of deaza- and aza-adenines in mixed ligand metal complexes

Cited by 38 publications

References 117 publications

Homoleptic Transition Metal Complexes of the 7-Azaindolide Ligand Featuring κ¹-N1 Coordination

Homoleptic Transition Metal Complexes of the 7-Azaindolide Ligand Featuring κ¹-N1 Coordination

Molecular recognition between adenine or 2,6-diaminopurine and copper(II) chelates with N,O2,S-tripodal tetradentate chelators having thioether or disulfide donor groups

Anion–Cation Recognition Pattern, Thermal Stability and DFT-Calculations in the Crystal Structure of H2dap[Cd(HEDTA)(H2O)] Salt (H2dap = H2(N3,N7)-2,6-Diaminopurinium Cation)

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Unravelling the versatile metal binding modes of adenine: Looking at the molecular recognition patterns of deaza- and aza-adenines in mixed ligand metal complexes

Cited by 38 publications

References 117 publications

Homoleptic Transition Metal Complexes of the 7-Azaindolide Ligand Featuring κ1-N1 Coordination

Homoleptic Transition Metal Complexes of the 7-Azaindolide Ligand Featuring κ1-N1 Coordination

Molecular recognition between adenine or 2,6-diaminopurine and copper(II) chelates with N,O2,S-tripodal tetradentate chelators having thioether or disulfide donor groups

Anion–Cation Recognition Pattern, Thermal Stability and DFT-Calculations in the Crystal Structure of H2dap[Cd(HEDTA)(H2O)] Salt (H2dap = H2(N3,N7)-2,6-Diaminopurinium Cation)

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Homoleptic Transition Metal Complexes of the 7-Azaindolide Ligand Featuring κ¹-N1 Coordination

Homoleptic Transition Metal Complexes of the 7-Azaindolide Ligand Featuring κ¹-N1 Coordination