Fluorine-19 nuclear magnetic resonance studies of diamagnetic fluoride complexes of nickel(IV), palladium(IV), and platinum(IV) in anhydrous hydrogen fluoride solutions

Matwiyoff, Nicholas A.; Asprey, L.B.; Wageman, William E.; Reisfeld, Martin J.; Fukushima, Eiji

doi:10.1021/ic50074a009

Cited by 25 publications

(7 citation statements)

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“…52,53 For nickel fluorides, 19 F NMR shifts are typically reported between −251 and −423 ppm. 54,55 In contrast to the fluoro complexes, the reported oxo complexes are purely hypothetical. Additionally, to the best of our knowledge, 17 O NMR shifts of group 10 oxo metal complexes are not reported.…”

Section: ■ Resultsmentioning

confidence: 98%

“…19 F NMR shifts of palladium fluoro complexes are typically found in the range of −274 to −323 ppm. ,− The example of a palladium difluoride with 19 F NMR shifts of −169 and −278 ppm, however, not only shows that the range of shifts is even greater but also shows that they can also drastically differ within the same complex . For platinum fluoro complexes, the range of 19 F NMR shifts is even greater and typically spans from −107 to −456 ppm. , For nickel fluorides, 19 F NMR shifts are typically reported between −251 and −423 ppm. , In contrast to the fluoro complexes, the reported oxo complexes are purely hypothetical. Additionally, to the best of our knowledge, 17 O NMR shifts of group 10 oxo metal complexes are not reported.…”

Section: Resultsmentioning

confidence: 99%

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Where Is the Fluoro Wall?: A Quantum Chemical Investigation

2020

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Despite their isoelectronic properties, fluoro and oxo ligands exhibit completely different chemical behavior. Formally speaking, the first is known to exclusively form single bonds, while the latter is generally observed to form double (or even triple) bonds. The biggest difference, however, lies in what is known among inorganic chemists as the Oxo Wall: the fact that six-coordinate tetragonal transition metal oxo complexes are not observed beyond group 7 elements. While the Oxo Wall was explained a few decades ago, some questions regarding the nature of the Oxo Wall remain unanswered. For example, why do group 8 oxo complexes with high oxidation states not violate the Oxo Wall? Moreover, why are transition metal fluoro complexes observed through the whole transition metal series? In order to understand how the small difference between these two isoelectronic ligands can give rise to such different chemical behaviors, we conducted an extensive computational analysis of the geometric and electronic properties of model fluoro and oxo complexes with metals around the Oxo Wall. Among many insights into the details of the Oxo Wall, we mostly learned that the oxygen 2p orbitals are prone to meaningfully interact with transition metal d orbitals, because they match not only spatially but also energetically, while for fluorine the p orbital energies are lower to an extent that interaction with transition metal d orbitals is much reduced. This in turn implies that in those instances where the metal d orbitals principally accessible for interaction are occupied, the oxygen 2p orbitals are too exposed to be stable.

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Section: ■ Resultsmentioning

confidence: 98%

Section: Resultsmentioning

confidence: 99%

Where Is the Fluoro Wall?: A Quantum Chemical Investigation

2020

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“…Concentrations of dinuclear palladium(II) complexes were 5 . 10 -5 mol/dm 3 . The electron absorption spectra were recorded in the wavelength range 200-500 nm at 25 o C and the experimental results were processed using the computer program Microsoft Office Excel 2003.…”

Section: Instrumental Methodesmentioning

confidence: 99%

“…Palladium(Ⅱ) complexes are interesting due to their similarity with the corresponding platinum(II) complexes, so they can be used as model molecules for investigation of the antitumor action mechanism of cisplatin and other platinum chemotherapeutics. Reactivity of palladium(Ⅱ) complexes is 10 4 -10 5 times higher in relation to analogous with platinum(II) (1)(2)(3)(4).…”

Section: Introductionmentioning

confidence: 96%

DNA-and BSA-Binding Studies of Dinuclear Palladium(II) Complexes with 1,5-Naphtiridine Bridging Ligands

Rajković

Franich

Cupurdija

et al. 2021

Serbian Journal of Experimental and Clinical Research

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The interactions of metal complexes with important biomolecules such as deoxyribonucleic acid (DNA) or bovine serum albumin (BSA) are responsible for their antitumor activity due to different modes of interaction with DNA and their transport through the blood system to cells and tissues via serum albumin. Therefore, the dinuclear palladium(II) complexes, [{Pd(en)Cl}2(μ-1,5- nphe)](NO3)2 (Pd1) and [{Pd(1,3-pd)Cl}2(μ-1,5-nphe)](NO3)2 (Pd2) (en is ethylenediamine, 1,3-pd is 1,3-propylenediamine and 1,5-nphe is the bridging 1,5-naphthyridine ligand) were synthesized and characterized by different spectroscopic methods. The UV-Vis and fluorescence emission spectroscopy were applied for evaluation of binding modes of Pd1 and Pd2 complexes to DNA as well as their interaction with BSA. The emission spectra indicate that the investigated Pd1 and Pd2 complexes can displace the ethidium bromide intercalator from DNA/EtBr molecules and act as intercalators showing strong interactions with DNA. The fluorescence intensity showes that Pd1 and Pd2 complexes can bind to BSA and then be transported to the cell.

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“…Other binary fluorides, exhibited no signals as the unpaired electronic spin density at the Fsites leads to strong line broadening and very fast nuclear spin relaxation as Fsites are bounded directly to paramagnetic ions. [51][52][53][54] Figure 7 shows the F-NMR spectra of 4-and 7-element containing fluoride powders (MEF4 and HEF7). It should be noted that the overall intensity for both samples is extremely small, compared to the spectra of the binary samples ( Figure S15), since all contributions are strongly broadened.…”

Section: Journal Of Materials Chemistry a Accepted Manuscriptmentioning

confidence: 99%