Detection and Characterization of Mononuclear Pd(I) Complexes

10.26434/chemrxiv.12470945 ◽

2020 ◽

Author(s):

Jia Luo ◽

Nigam P. Rath ◽

Liviu M. Mirica

Keyword(s):

Dft Calculations ◽

Chemical Reduction ◽

Spectroscopic Studies ◽

Oxidation States ◽

Chemical Transformations ◽

X Ray ◽

Tetradentate Ligands ◽

The Stability ◽

X Ray Absorption

Palladium is a versatile transition metal used to catalyze a large number of chemical transformations, largely due to its ability to access various oxidation states (0, I, II, III, and IV). Among these oxidation states, Pd(I) is arguably the least studied, and while dinuclear Pd(I) complexes are more common, mononuclear Pd(I) species are very rare. Reported herein are spectroscopic studies of a series of Pd(I) intermediates generated by the chemical reduction of Pd(II) precursors supported by the tetradentate ligands 2,11-dithia[3.3](2,6)pyridinophane (N2S2) and N,N’-di-tert-butyl-2,11-diaza[3.3](2,6)pyridinophane (tBuN4): [(N2S2)PdII(MeCN)]2(OTf)4 (1), [(N2S2)PdIIMe]2(OTf)2 (2), [(N2S2)PdIICl](OTf) (3), [(N2S2)PdIIX](OTf)2 (X = tBuNC 4, PPh3 5), [(N2S2)PdIIMe(PPh3)](OTf) (6), and [(tBuN4)PdIIX2](OTf)2 (X = MeCN 8, tBuNC 9). In addition, a stable Pd(I) dinuclear species, [(N2S2)PdI(m-tBuNC)]2(ClO4)2 (7), was isolated upon the electrochemical reduction of 4 and structurally characterized. Moreover, the (tBuN4)PdI intermediates, formed from the chemical reduction of [(tBuN4)PdIIX2](OTf)2 (X = MeCN 8, tBuNC 9) complexes, were investigated by EPR spectroscopy, X-ray absorption spectroscopy (XAS), and DFT calculations, and compared with the analogous (N2S2)PdI systems. Upon probing the stability of Pd(I) species under various ligand environments (N2S2 and tBuN4), it is apparent that the presence of soft ligands such as tBuNC and PPh3 significantly improves the stability of Pd(I) species, which should make the isolation of mononuclear Pd(I) species possible.

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Cu+-specific CopB transporter: Revising P1B-type ATPase classification

Proceedings of the National Academy of Sciences ◽

10.1073/pnas.1721783115 ◽

2018 ◽

Vol 115 (9) ◽

pp. 2108-2113 ◽

Cited By ~ 15

Author(s):

Rahul Purohit ◽

Matthew O. Ross ◽

Sharon Batelu ◽

April Kusowski ◽

Timothy L. Stemmler ◽

...

Keyword(s):

Maximal Activity ◽

Spectroscopic Characterization ◽

Spectroscopic Studies ◽

Divalent Metal Ions ◽

X Ray ◽

Reducing Environment ◽

Methionine Residues ◽

Cellular Copper ◽

X Ray Absorption

The copper-transporting P1B-ATPases, which play a key role in cellular copper homeostasis, have been divided traditionally into two subfamilies, the P1B-1-ATPases or CopAs and the P1B-3-ATPases or CopBs. CopAs selectively export Cu+ whereas previous studies and bioinformatic analyses have suggested that CopBs are specific for Cu2+ export. Biochemical and spectroscopic characterization of Sphaerobacter thermophilus CopB (StCopB) show that, while it does bind Cu2+, the binding site is not the prototypical P1B-ATPase transmembrane site and does not involve sulfur coordination as proposed previously. Most important, StCopB exhibits metal-stimulated ATPase activity in response to Cu+, but not Cu2+, indicating that it is actually a Cu+ transporter. X-ray absorption spectroscopic studies indicate that Cu+ is coordinated by four sulfur ligands, likely derived from conserved cysteine and methionine residues. The histidine-rich N-terminal region of StCopB is required for maximal activity, but is inhibitory in the presence of divalent metal ions. Finally, reconsideration of the P1B-ATPase classification scheme suggests that the P1B-1- and P1B-3-ATPase subfamilies both comprise Cu+ transporters. These results are completely consistent with the known presence of only Cu+ within the reducing environment of the cytoplasm, which should eliminate the need for a Cu2+ P1B-ATPase.

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EXELFS Studies of Carbon Fibers

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100133953 ◽

1990 ◽

Vol 48 (2) ◽

pp. 72-73

Author(s):

V. Serin ◽

K. Hssein ◽

G. Zanchi ◽

J. Sévely

Keyword(s):

Carbon Fibers ◽

Energy Analysis ◽

Electron Excitation ◽

Complex Structures ◽

High Modulus ◽

Promising Technique ◽

X Ray ◽

Fine Structures ◽

X Ray Absorption

The present developments of electron energy analysis in the microscopes by E.E.L.S. allow an accurate recording of the spectra and of their different complex structures associated with the inner shell electron excitation by the incident electrons (1). Among these structures, the Extended Energy Loss Fine Structures (EXELFS) are of particular interest. They are equivalent to the well known EXAFS oscillations in X-ray absorption spectroscopy. Due to the EELS characteristic, the Fourier analysis of EXELFS oscillations appears as a promising technique for the characterization of composite materials, the major constituents of which are low Z elements. Using EXELFS, we have developed a microstructural study of carbon fibers. This analysis concerns the carbon K edge, which appears in the spectra at 285 eV. The purpose of the paper is to compare the local short range order, determined by this way in the case of Courtauld HTS and P100 ex-polyacrylonitrile carbon fibers, which are high tensile strength (HTS) and high modulus (HM) fibers respectively.

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MOLECULAR AND ELECTRONIC STRUCTURE OF HYDROLIZED PLATINUM ANTICANCER DRUGS REVEALED BY X-RAY ABSORPTION, IR, UV-VIS SPECTROSCOPIES AND DFT CALCULATIONS

Журнал структурной химии ◽

10.15372/jsc20160724 ◽

2016 ◽

Keyword(s):

Electronic Structure ◽

Dft Calculations ◽

Anticancer Drugs ◽

X Ray ◽

Platinum Anticancer Drugs ◽

X Ray Absorption ◽

Molecular And Electronic Structure

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Database of ab initio L-edge X-ray absorption near edge structure

Scientific Data ◽

10.1038/s41597-021-00936-5 ◽

2021 ◽

Vol 8 (1) ◽

Author(s):

Yiming Chen ◽

Chi Chen ◽

Chen Zheng ◽

Shyam Dwaraknath ◽

Matthew K. Horton ◽

...

Keyword(s):

High Throughput ◽

Scattering Theory ◽

Research Community ◽

Metal Compounds ◽

Edge Structure ◽

X Ray ◽

Initial Release ◽

Computational Workflow ◽

X Ray Absorption

AbstractThe L-edge X-ray Absorption Near Edge Structure (XANES) is widely used in the characterization of transition metal compounds. Here, we report the development of a database of computed L-edge XANES using the multiple scattering theory-based FEFF9 code. The initial release of the database contains more than 140,000 L-edge spectra for more than 22,000 structures generated using a high-throughput computational workflow. The data is disseminated through the Materials Project and addresses a critical need for L-edge XANES spectra among the research community.

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Characterization of Silver Binding in Cryptomelane by X-ray Absorption Spectroscopy

MRS Proceedings ◽

10.1557/proc-524-353 ◽

1998 ◽

Vol 524 ◽

Cited By ~ 4

Author(s):

R. Ravikumar ◽

D. W. Fuerstenau ◽

G. A. Waychunas

Keyword(s):

Manganese Oxide ◽

Silver Ions ◽

Oxide Phase ◽

Synthetic Sample ◽

Temperature Spectrum ◽

X Ray ◽

Room Temperature Sample ◽

X Ray Absorption ◽

Temperature Sample

ABSTRACTUsing silver K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy, two different samples of silver-containing manganese oxide were analyzed in the fluorescence mode. For the first sample, silver ions from solution were sorbed onto one synthetic manganese oxide phase, namely cryptomelane (KxMn8O16, where l<x<2). The second sample was a silvermanganese oxide from Colorado. From the EXAFS analysis, silver was found to occupy two different sites in the synthetic sample. The natural samples from Colorado also exhibited a very similar coordination distances as the synthetic samples. In the low temperature spectrum of the synthetic sample at 10 K, the Ag-O peak was found to be missing and the amplitude of the Ag- Ag peak was approximately three times larger than the corresponding room temperature sample.

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