Über Kaliumtetracyanoplatinat(II), Kaliumtetracyanopalladat(II) und deren Monohydrate

Mühle, Claus; Nuß, Jürgen; Dinnebiér, Robert E.; Jansen, Martin

doi:10.1002/zaac.200400148

Cited by 18 publications

(16 citation statements)

References 18 publications

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“…(6) www.chemeurj.org part of the negative charge that results from deprotonation of the N1 site is delocalized onto the guanine ring rather than located in the Pt À N1 bond. anions in the characteristic side-on fashion, [25,26] with K À C distances exceeding K À N distances, or binding in a monodentate fashion through N atoms of [Pt(CN) 4 ] 2À anions. [26] Of the three K + ions in the asymmetric unit, one (K2) is associated exclusively with [Pt(CN) 4 ] 2À anions (three side-on contacts, two end-on contacts) and a water molecule.…”

Section: Crystal Structure Analysis Of {Trans-mentioning

confidence: 99%

“…anions in the characteristic side-on fashion, [25,26] with K À C distances exceeding K À N distances, or binding in a monodentate fashion through N atoms of [Pt(CN) 4 ] 2À anions. [26] Of the three K + ions in the asymmetric unit, one (K2) is associated exclusively with [Pt(CN) 4 ] 2À anions (three side-on contacts, two end-on contacts) and a water molecule. A second K + ion (K1) is bonded to O6 of a guaninate ligand in a monodentate fashion, and in addition to four cyanido ligands (one side-on contact, three end-on contacts) as well as two water molecules.…”

Section: Crystal Structure Analysis Of {Trans-mentioning

confidence: 99%

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Pt^II Coordination to N1 of 9‐Methylguanine: Why it Facilitates Binding of Additional Metal Ions to the Purine Ring

Müller¹,

Shen²,

Miguel³

et al. 2011

Chemistry A European J

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The preparation and X-ray crystal structure analysis of {trans-[Pt(MeNH(2))(2)(9-MeG-N1)(2)]}⋅{3 K(2)[Pt(CN)(4)]}⋅6 H(2)O (3 a) (with 9-MeG being the anion of 9-methylguanine, 9-MeGH) are reported. The title compound was obtained by treating [Pt(dien)(9-MeGH-N7)](2+) (1; dien=diethylenetriamine) with trans-[Pt(MeNH(2))(2)(H(2)O)(2)](2+) at pH 9.6, 60 °C, and subsequent removal of the [(dien)Pt(II)] entities by treatment with an excess amount of KCN, which converts the latter to [Pt(CN)(4)](2-). Cocrystallization of K(2)[Pt(CN)(4)] with trans-[Pt(MeNH(2))(2)(9-MeG-N1)(2)] is a consequence of the increase in basicity of the guanine ligand following its deprotonation and Pt coordination at N1. This increase in basicity is reflected in the pK(a) values of trans-[Pt(MeNH(2))(2)(9-MeGH-N1)(2)](2+) (4.4±0.1 and 3.3±0.4). The crystal structure of 3 a reveals rare (N7,O6 chelate) and unconventional (N2,C2,N3) binding patterns of K(+) to the guaninato ligands. DFT calculations confirm that K(+) binding to the sugar edge of guanine for a N1-platinated guanine anion is a realistic option, thus ruling against a simple packing effect in the solid-state structure of 3 a. The linkage isomer of 3 a, trans-[Pt(MeNH(2))(2)(9-MeG-N7)(2)] (6 a) has likewise been isolated, and its acid-base properties determined. Compound 6 a is more basic than 3 a by more than 4 log units. Binding of metal entities to the N7 positions of 9-MeG in 3 a has been studied in detail for [(NH(3))(3)Pt(II)], trans-[(NH(3))(2)Pt(II)], and [(en)Pd(II)] (en=ethylenediamine) by using (1)H NMR spectroscopy. Without exception, binding of the second metal takes place at N7, but formation of a molecular guanine square with trans-[(Me(2)NH(2))Pt(II)] cross-linking N1 positions and trans-[(NH(3))(2)Pt(II)] cross-linking N7 positions could not be confirmed unambiguously, despite the fact that calculations are fully consistent with its existence.

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Section: Crystal Structure Analysis Of {Trans-mentioning

confidence: 99%

Section: Crystal Structure Analysis Of {Trans-mentioning

confidence: 99%

Pt^II Coordination to N1 of 9‐Methylguanine: Why it Facilitates Binding of Additional Metal Ions to the Purine Ring

Müller¹,

Shen²,

Miguel³

et al. 2011

Chemistry A European J

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“…n CN data taken from the IR spectra and reference data from the literature. [23,24] n 4 ] indicates that cyanide ions are incorporated into the metallopeptide and a stable adduct is formed. The nickel-bound cyanide ion now possesses a dipolar interaction to a proton.…”

mentioning

confidence: 99%

“…[30] This effect is also observed in K 2 [Pd(CN) 4 ], which possesses the same crystal structure as K 2 [Ni(CN) 4 ]. [24] The question now is how many cyanide ions bind to the [NiA C H T U N G T R E N N U N G (mSOD)] peptide. The square-planar local environment of the Ni center implies that, in principle, up to two cyanide ions could bind to the [NiA C H T U N G T R E N N U N G (mSOD)], one above and one below the local symmetry plane.…”

mentioning

confidence: 99%

New Insight into the Mode of Action of Nickel Superoxide Dismutase by Investigating Metallopeptide Substrate Models

Tietze

Breitzke

Imhof³

et al. 2008

Chemistry A European J

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For the first time, the existence of a substrate adduct of a nickel superoxide dismutase (NiSOD) model, based on the first nine residues from the N terminus of the active form of Streptomyces coelicolor NiSOD, has been proven and the adduct has been isolated. This adduct is based on the cyanide anion (CN(-)), as a substrate analogue of the superoxide anion (O(2)(*-)), and the nickel metallopeptide H-HCDLPCGVY-NH(2)-Ni. Spectroscopic studies, including IR, UV/Vis, and liquid- and solid-state NMR spectroscopy, show a single nickel-bound cyanide anion, which is embedded in the metallopeptide structure. This complex sheds new light on the question of whether the mode of action of the NiSOD enzyme is an inner- or outer-sphere mechanism. Whereas discussion was previously biased in favor of an outer-sphere electron-transfer mechanism due to the fact that binding of cyanide or azide moieties to the nickel active site had never been observed, our results are a clear indication in favor of the inner-sphere electron-transfer mechanism for the disproportionation of the O(2)(*-) ion, whereby the substrate is attached to the Ni atom in the active site of the NiSOD.

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“…In such compounds a metalmetal bond is realized due to overlapping d z 2 orbitals of platinum atoms [23]. The shortest Pt-Pt distance in КСР compounds falls in the range 2.80-3.00 Å [24], which is comparable to the length of the metal-metal The adsorbed compound with the Pt4f 7/2 binding energy of 75.0 eV formally corresponds to a platinum complex with a Pt(III)-Pt(III) bond. It is known that a rather stable dinuclear anion [Pt 2 (CN) 10 ] 4-with a Pt(III)-Pt(III) bond can be formed on the oxidation of the [Pt(CN) 4 ] 2-complex anion by Tl(III) cyanide compounds [17,25,26] or on the electrochemical reducetion of aqueous solutions containing Cu 2+ and [Pt(CN) 6 ] 2-ions [18].…”

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confidence: 98%

Study of sorption of platinum and palladium cyanometallate complexes as the key to understanding the mechanism of binding the [Au(CN)2]− anion with carbon adsorbents

Vorob'ev-Desyatovskii¹,

Kubyshkin²,

Ibragimova³

et al. 2012

Russ J Gen Chem

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Goldcarb WSC-207C GR activated carbons with platinum and palladium complexes adsorbed from aqueous solutions of K 2 [Pt(CN) 4 ], K 2 [Pt(CN) 6 ], and K 2 [Pd(CN) 4 ] were studied by the methods of X-ray photoelectron spectroscopy and IR spectroscopy with Fourier transformation, and also by MALDI massspectrometry. Platinum and palladium cyanide complexes are not reduced onto surface of active charcoal while adsorption. A certain part of the [Pd(CN) 4 ] 2-and [Pt(CN) 4 ] 2-anions directly bound to active centers on the activated carbon is oxidized more deeply and functions as particles-anchors, forming oligomers resembling Krogmann salt. A correspondence between the structure of the complex cyanometallate ion and a mode of its binding with active carbon is found. The adsorption of complex species with a linear structure or a square planar structure is defined by a possibility of the formation of donor-acceptor and metallophilic bonds. The mode of the anion [Au(CN) 2 ] -binding with the surface of active carbon was considered.In last 30 years a stable interest arose to the application of activated carbons in hydrometallurgical processes. First of all, it is connected with industrial usage of coals as main adsorbents for extraction of gold(I) from cyanide solutions and pulps. In spite of it the reason of a selective sorption of gold(I) cyanide complex on carbon adsorbents is not yet elucidated at present. Unlike the corresponding complexes of gold, adsorption of platinum and palladium cyanide complexes is by no means studied though the knowledge of specificity of their behavior in relation to carbon adsorbents can present both theoretical and practical interest. This interest is connected, firstly, with the study of mechanisms of binding complexes of noble metals with active carbons and also with the search for methods improving kinetic and capacity properties of carbon adsorbents and increasing their selectivity. Results of such studies promote the improvement of the process of mining and refining platinum metals and gold.Depending on the nature of a central atom and its ligand environment, and also on the composition of a solution and conditions, in which transition metal complexes contact carbon adsorbents, partial or complete reduction of a metal center and (or) chemisorption, which is accompanied by a change in its oxidation state, can occur at the adsorption. To predict a possible result of the interaction between activated carbon and complexes of noble metals, it was suggested to use a comparison of working and stationary potentials of coal in a solution with appropriate redox potentials of complex compounds [1]. The nature of adsorbate at the adsorption of transition metal complex compounds on activated carbons depends on several factors. The composition

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Über Kaliumtetracyanoplatinat(II), Kaliumtetracyanopalladat(II) und deren Monohydrate

Cited by 18 publications

References 18 publications

Pt^II Coordination to N1 of 9‐Methylguanine: Why it Facilitates Binding of Additional Metal Ions to the Purine Ring

Pt^II Coordination to N1 of 9‐Methylguanine: Why it Facilitates Binding of Additional Metal Ions to the Purine Ring

New Insight into the Mode of Action of Nickel Superoxide Dismutase by Investigating Metallopeptide Substrate Models

Study of sorption of platinum and palladium cyanometallate complexes as the key to understanding the mechanism of binding the [Au(CN)2]− anion with carbon adsorbents

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Über Kaliumtetracyanoplatinat(II), Kaliumtetracyanopalladat(II) und deren Monohydrate

Cited by 18 publications

References 18 publications

PtII Coordination to N1 of 9‐Methylguanine: Why it Facilitates Binding of Additional Metal Ions to the Purine Ring

PtII Coordination to N1 of 9‐Methylguanine: Why it Facilitates Binding of Additional Metal Ions to the Purine Ring

New Insight into the Mode of Action of Nickel Superoxide Dismutase by Investigating Metallopeptide Substrate Models

Study of sorption of platinum and palladium cyanometallate complexes as the key to understanding the mechanism of binding the [Au(CN)2]− anion with carbon adsorbents

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Pt^II Coordination to N1 of 9‐Methylguanine: Why it Facilitates Binding of Additional Metal Ions to the Purine Ring

Pt^II Coordination to N1 of 9‐Methylguanine: Why it Facilitates Binding of Additional Metal Ions to the Purine Ring