Importance of platinum(II)-assisted platinum(IV) substitution for the oxidation of guanosine derivatives by platinum(IV) complexes

Guanosine derivatives with a nucleophilic group at the 5' position (G-5') are oxidized by the Pt (IV) complex Pt( d, l)(1,2-(NH 2) 2C 6H 10)Cl 4 ([Pt (IV)(dach)Cl 4]). The overall redox reaction is autocatalytic, consisting of the Pt (II)-catalyzed Pt (IV) substitution and two-electron transfer between Pt (IV) and the bound G-5'. In this paper, we extend the study to improve understanding of the redox reaction, particularly the substitution step. The [Pt (II)(NH 3) 2(CBDCA-O,O')] (CBDCA = cyclobutane-1,1-dicarboxylate) complex effectively accelerates the reactions of [Pt (IV)(dach)Cl 4] with 5'-dGMP and with cGMP, indicating that the Pt (II) complex does not need to be a Pt (IV) analogue to accelerate the substitution. Liquid chromatography/mass spectroscopy (LC/MS) analysis showed that the [Pt (IV)(dach)Cl 4]/[Pt (II)(NH 3) 2(CBDCA-O,O')]/cGMP reaction mixture contained two Pt (IV)cGMP adducts, [Pt (IV)(NH 3) 2(cGMP)(Cl)(CBDCA-O,O')] and [Pt (IV)(dach)(cGMP)Cl 3]. The LC/MS studies also indicated that the trans, cis-[Pt (IV)(dach)( (37)Cl) 2( (35)Cl) 2]/[Pt (II)(en)( (35)Cl) 2]/9-EtG mixture contained two Pt (IV)-9-EtG adducts, [Pt (IV)(en)(9-EtG)( (37)Cl)( (35)Cl) 2] and [Pt (IV)(dach)(9-EtG)( (37)Cl)( (35)Cl) 2]. These Pt (IV)G products are predicted by the Basolo-Pearson (BP) Pt (II)-catalyzed Pt (IV)-substitution scheme. The substitution can be envisioned as an oxidative addition reaction of the planar Pt (II) complex where the entering ligand G and the chloro ligand from the axial position of the Pt (IV) complex are added to Pt (II) in the axial positions. From the point of view of reactant Pt (IV), an axial chloro ligand is thought to be substituted by the entering ligand G. The Pt (IV) complexes without halo axial ligands such as trans, cis-[Pt(en)(OH) 2Cl 2], trans, cis-[Pt(en)(OCOCF 3) 2Cl 2], and cis, trans, cis-[Pt(NH 3)(C 6H 11NH 2)(OCOCH 3) 2Cl 2] ([Pt (IV)(a,cha)(OCOCH 3) 2Cl 2], satraplatin) did not react with 5'-dGMP. The bromo complex, [Pt (IV)(en)Br 4], showed a significantly faster substitution rate than the chloro complexes, [Pt (IV)(en)Cl 4] and [Pt (IV)(dach)Cl 4]. The results indicate that the axial halo ligands are essential for substitution and the Pt (IV) complexes with larger axial halo ligands have faster rates. When the Pt (IV) complexes with different carrier ligands were compared, the substitution rates increased in the order [Pt (IV)(dach)Cl 4] < [Pt (IV)(en)Cl 4] < [Pt (IV)(NH 3) 2Cl 4], which is in reverse order to the carrier ligand size. These axial and carrier ligand effects on the substitution rates are consistent with the BP mechanism. Larger axial halo ligands can form a better bridging ligand, which facilitates the electron-transfer process from the Pt (II) to Pt (IV) center. Smaller carrier ligands exert less steric hindrance for the bridge formation.     

Extraction of platinum with Astrafloxin FF from aqueous-organic solutions: Separative extraction-spectrophotometric determination of platinum(II) and platinum(IV) species

The optimum conditions of the extraction of the ion associates of platinum with the thiocyanate ions and the polymethine basic dye Astrafloxin FF by aromatic hydrocarbons and acetic acid esters from aqueous and aqueous-organic solutions were studied. The introduction of water-soluble donor-active solvents (hexamethylphosphoric triamide, N,N-diethylacetamide, N,N-dimethylformamide, and N,N-diethylformamide) leads to a considerable increase in the extraction of the ion associates of platinum and the simultaneous suppression of the extraction of the simple dye salt. The molar absorption coefficients of the extracts of ion associates are as high as (8.1?C13.3) × 10⁴. 84?C96% platinum is extracted in the form of ion associates by a single extraction. The conversion of platinum into ion associates makes it possible to separate platinum from many elements, including Cu, Cd, Ni, Co, Cr, Pb, In, Ag, Pd, Ir, Rh, and Ru, by extraction. In this case, platinum(II) is extracted in the form of ion associates under standard conditions, whereas platinum(IV) is extracted only after the preliminary thermal treatment of the test sample. A new procedure was developed for the extraction-spectrophotometric determination of the trace amounts of platinum(II) and platinum(IV), in particular, in their mixtures.     

Cyclometallated platinum(II) complexes: oxidation to, and C-H activation by, platinum(IV)

A series of cyclometallated phenylpyridine platinum(II) complexes have been synthesised with a systematic variation in both the phenylpyridine and the ancillary ligand. Oxidation of one of the cyclometallated species leads to a number of isomeric platinum(IV) complexes, all of which eventually isomerize to a single compound. The route to these new compounds has been demonstrated to involve an initial slow oxidation followed by a rapid C-H activation to give doubly cyclometallated complexes. The solid state structures of a number of both the platinum(II) and the platinum(IV) species have been solved; many of the structures exhibited extended interactions that result in complex three dimensional packing.     

N-aminorhodamne complexes of palladium(II), palladium(IV) and platinum(II)

Summary TheN-aminorhodanine (L) complexes: PdLX, (X = Br or I), ML_1.5Cl₂ (M = Pd or Pt), PtL₂X₂ (X = Br, I or ClO₄), PdL₃(ClO₄)₂, PdL_1.5Cl₄ and PdL₃(ClO₄)₄ have been prepared and investigated. The ligand is bonded to the metal ion through the aminic nitrogen atom as monodentate or through this atom and the thiocarbonylic sulphur atom when it acts as chelating or bridging ligand. The carbonylic oxygen atom is never coordinated.     

Palladium(II) and platinum(II),(IV) complexes of 2-aminopyrimidine derivatives

Palladium(II) and Platinum(II),(IV) complexes with 2-aminopyrimidine derivatives (L1)–(L3), prepared by reacting the corresponding metal halide with the ligand in the required stoichiometric ratio, were characterised by chemical analyses and physical measurements. The structures have been assigned on the basis of i.r. spectroscopy, electronic reflectance spectra and molar conductivities.     

Facile generation of platinum(IV) compounds with mixed labile moieties. Hydrogen peroxide oxidation of platinum(II) to platinum(IV) compounds

Hydrogen peroxide oxidation of platinum(II) compounds containing labile groups such as Cl, OH, and alkene moieties has been carried out and the products characterized. The reactions of [Pt^II (X)₂ (N–N)] (X = Cl, OH, X₂ = isopropylidenemalorate (ipm); N–N 2,2-dimethyl-1,3-propanediamine [(dmpda), N-isopropyl-1,3-propanediamine (ippda)] with hydrogen peroxide in an appropriate solvent at room temperature affords [Pt^IV (OH)(Y)(X)₂(N–N)] (Y = OH, OCH₃). The crystal structures of [Pt^IV(OH)(OCH₃)(Cl)₂(dmpda)]·2H₂O (P-1 bar, a = 6.339(2) Å , b = 9.861(1) Å, c = 11.561(1) Å, a = 92.078(9)°, β = 104.78(1)°, γ=100.54(1)°, V = 684.3(2) ų, Z = 2R = 0.0503) and [Pt^IV(OH)₂(ipm)(ippda)]·3H₂O (C 2/c, a = 27.275(6) Å, b=6.954(2) Å, c = 22.331(4) Å, β = 118.30(2)°, V = 3729(2) ų, Z = 8, R = 0.0345) have been solved and refined. The local geometry around the platinum(IV) atom approximates to a typical octahedral arrangement with two added groups (OH and OCH₃; OH and OH) in a transposition. The platinum(IV) compounds with potential labile moieties may be important intermediate species for further reactions.     

Spectrophotometric determination of osmium(IV), iridium(IV) and platinum(iv) and separation and determination of palladium(II) and ruthenium(III) in the presence of other platinum metals, with oximidobenzotetronic acid as reagent

Oximidobenzotetronic acid is suggested as a reagent for the spectrophotometric determination of osmium(IV), iridium(III), iridium(IV), platinum(IV) and for separation and determination of palladium(II) and ruthenium(III) in the presence of other platinum metals. Iridium(III) and (IV) can be estimated when present together.     

Simultaneous determination of uranium(IV) and iron(II) with a stopped-flow inductive kinetic spectrophotometric method

A kinetic method for simultaneous determination of multielements is proposed, and a procedure for simultaneous determination of uranium(VI) and iron(II) is established based on their inductive effect on the chromium(VI)-iodide redox reaction in weak acidic medium. The reaction was monitored with the stopped-flow spectrophotometric technique by using I ₃ ^– -starch complex as indicator. The calibration graphs are linear for 0–3.6 g.cm^–3 U(IV), and 0–2.5 g.cm^–3 Fe(II), respectively. Most foreign ions, except for V(IV), Sb(III), do not interfere with the determination.     

Kinetics of the homogeneous oxidation of hydrogen by platinum(II) and platinum(IV) chloro complexes in aqueous solution

The kinetics of the homogeneous oxidation of hydrogen in the Pt(II)–Pt(IV)–Cl^––H₂O system has been studied for the first time in conditions permitting to avoid the formation of Pt-black. It is shown that platinum (II) [Pt(II)Cl_i(H₂O)_4-i, where i=1, 2, 2], is active in the reaction, whereas the PtCl ₄ ^2– complex and platinum(IV) do not react with hydrogen.

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, Pt-, H₂ Pt^II–Pt^IV–Cl^––H₂O. (II) (Pt^IICl_i(H₂O)_4-i, i=1, 2, 3); PtCl ₄ ^2– (IV) .

     

Novel platinum(II) and (IV) complexes of naphthaldimine schiff bases

Naphthaldimines containing N₂O₂ donor centers react with platinum(II) and (IV) chlorides to give two types of complexes depending on the valence of the platinum ion. For [Pt(II)], the ligand is neutral, [(H₂L¹)PtCl₂]·3H₂O (1) and [(H₂L³)₂Pt₂Cl₄]·5H₂O (3), or monobasic [(HL²)₂Pt₂Cl₂]·2H₂O (2) and [(HL⁴)₂Pt]·2H₂O (4). These complexes are all diamagnetic having square-planar geometry. For [Pt(IV)], the ligand is dibasic, [(L¹)Pt₂Cl₄(OH)₂]·2H₂O (5), [(L²)Pt₃Cl₁₀]·3H₂O (6), [(L³)Pt₂Cl₄(OH)₂]·C₂H₅OH (7) and [(L⁴)Pt₂Cl₆]·H₂O (8). The Pt(IV) complexes are diamagnetic and exhibit octahedral configuration around the platinum ion. The complexes were characterized by elemental analysis, UV-Vis and IR spectra, electrical conductivity and thermal analyses (DTA and TGA). The molar conductances in DMF solutions indicate that the complexes are non-ionic. The complexes were tested for their catalytic activities towards cathodic reduction of oxygen.     

Sorption recovery of platinum(II) and platinum(IV) chloro complexes with a heterochain sulfur-containing sorbent

The recovery of platinum(II) and platinum(IV) chloro complexes from hydrochloric acid and chloride solutions with a new heterochain S,N-containing sorbent, MITKhAT, was studied. The suggested mechanism of formation of platinum(II) mercapto-thio ether complexes in the course of sorption was confirmed by DFT calculations. The results of group and selective recovery of platinum metals with MITKhAT sorbent from simulated and real industrial solutions are reported.     

The crystal and molecular structure of two pyridium propylide complexes of platinum(II) and platinum(IV)

Single crystal structure analyses have been completed of dichloro(pydridinum propylide)pyridineplatinum(II) and tetrachloro(pyridinium propylide)pyridine-platinum(IV). C₁₃H₁₆Cl₂N₂Pt forms monoclinic crystals from benzene and an X-ray analysis has been based on 1560 independent reflexions, intensities of which were measured on a Pailread diffractometer; least-quarters analysis of atomic parameters of the two independent molecules in the unit cell has converged R = 0.097. C₃H₁₆Cl₄N₂Pt·CHCl₃ also forms monoclinic crystals and an analysis is based on 1913 reflecxions (R = 0.089), intensities of which were visually estimated from Weissenberg and precession photographs. The mean metal-ligand band lenghts are 2.32 » (Pt-Cl), 2.10 » (Pt-N), 2.01 » (Pt-C) and are independent of the formal oxidations state of the metal. The formulation of the complexes as containing co-ordinated ylides is based on both NMR and stereochemical data.     

Simultaneous determination of uranium(IV) and thorium(IV) ions with Arsenazo III by partial least squares method

A multivariate calibration method, Partial Least Squares Type 1 (PLS-1), is proposed for simultaneous spectrophotometric determination of uranium and thorium ions as their complexes with arsenazo III in hydrochloric acid medium. Several data characteristics are taking into account in order to minimize the optimum number of factors required for the construction of calibration model, while using various statistical criterions of selection. Finally, the evaluated calibration model is satisfactorily applied to determination of these ions in samples that resemble sulfuric acid leach solution obtained from a uranium ore.     

Synthesis, X-ray crystallographic, and NMR characterizations of platinum(II) and platinum(IV) pyrophosphato complexes

A series of mononuclear cis-diamineplatinum(II) pyrophosphato complexes containing ammine (am), trans-1,2-cyclohexanediamine (dach), and 1,2-ethanediamine (en) as the amine ligands were synthesized and characterized by (31)P and (195)Pt NMR spectroscopy. Chemical shifts of (31)P NMR resonances of these completely deprotonated complexes appear at 2.12, 1.78, and 1.93 ppm, indicating a coordination chemical shift of at least 8 ppm. The (195)Pt NMR chemical shifts for the am and dach complexes were observed at -1503 and -1729 ppm. The complexes are highly stable at neutral pH; no aquation due to the release of either phosphate or amine ligands was observed within 48 h. Furthermore, no partial deligation of the pyrophosphate ligand was detected within several days at neutral pH. At lower pH, however, release of a pyrophosphate ion was observed with concomitant formation of a bridged pyrophosphatoplatinum(II) dinuclear complex. The extended crystal structure containing the dach ligand revealed a zigzag chain stacked in a head-to-tail fashion. Moreover, two zigzag chains are juxtaposed in a parallel fashion and supported by additional hydrogen bonds reminiscent of DNA structures where two strands of DNA bases are held by hydrogen bonds. Theoretical calculations support the notion that the two dinuclear units are held together primarily by hydrogen bonds between the amine and phosphate moieties. Platinum(II) pyrophosphato complexes were readily oxidized by hydrogen peroxide to yield cis-diamine-trans-dihydroxopyrophosphatoplatinum(IV) complexes. Two of these complexes, containing am and en, were characterized by X-ray crystallography. Notable structural features include Pt-O (phosphate) bond distances of 2.021-2.086 A and departures from 180 degrees in trans-HO-Pt-OH bond angles, >90 degrees in O-Pt-O, and >90 degrees in cis-N-Pt-N bond angles. The departure in the trans-HO-Pt-OH angle is more pronounced in the 1,2-ethanediamine complex compared to the dach analogue because of the existence of two molecules possessing enantiomeric conformations within the asymmetric unit. (31)P NMR spectra exhibited well-resolved (195)Pt satellites with coupling constants of 15.4 Hz for the ammine and 25.9 Hz for both the 1,2-ethanediamine and trans-1,2-cyclohexanediamine complexes. The (195)Pt NMR spectrum of the ammine complex clearly showed coupling with two equivalent N atoms.