Stibine as a reagent in molecular chemistry - targeted synthesis of primary and secondary stibanyl-gallanes and their lighter homologues

2021 ◽  
Vol 57 (31) ◽  
pp. 3781-3784
Author(s):  
Selina Schneider ◽  
Sergei Ivlev ◽  
Carsten von Hänisch
Keyword(s):  
Oxidative Addition ◽  
Gallium Atom ◽  
Molecular Chemistry ◽  
First Time

For the first time, SbH3 has been successfully used as a synthon in molecular chemistry. The reaction of SbH3 with (Dipp2NacNac)Ga proceeds under the oxidative addition of a Sb–H bond to the gallium atom.

Single-step conversion of silathiogermylene to germaacid anhydrides: unusual reactivity

2015 ◽  
Vol 51 (20) ◽  
pp. 4310-4313 ◽  
Author(s):  
Surendar Karwasara ◽  
Dhirendra Yadav ◽  
Chandan Kumar Jha ◽  
Gopalan Rajaraman ◽  
Selvarajan Nagendran
Keyword(s):  
Oxidative Addition ◽  
Single Step ◽  
First Time

Single-step conversion of germylene (2) to germaacid anhydrides (3 and 4) is achieved through oxidative-addition with S/Se that involves condensation for the first time.

scholarly journals Direct Base-Assisted C‒H Cyclonickelation of 6-Phenyl-2,2′-bipyridine

Molecules ◽  
2020 ◽  
Vol 25 (4) ◽  
pp. 997
Author(s):  
Nicolas Vogt ◽  
Vasily Sivchik ◽  
Aaron Sandleben ◽  
Gerald Hörner ◽  
Axel Klein
Keyword(s):  
Elevated Temperature ◽  
Title Compound ◽  
Noble Metals ◽  
Oxidative Addition ◽  
Base Metals ◽  
Base Pairs ◽  
Reaction Conditions ◽  
Wide Range ◽  
The World ◽  
First Time

The organonickel complexes [Ni(Phbpy)X] (X = Br, OAc, CN) were obtained for the first time in a direct base-assisted arene C(sp2)–H cyclometalation reaction from the rather unreactive precursor materials NiX2 and HPhbpy (6-phenyl-2,2′-bipyridine) or from the versatile precursor [Ni(HPhbpy)Br2]2. Different from previously necessary C‒Br oxidative addition at Ni(0), an extended scan of reaction conditions allowed quantitative access to the title compound from Ni(II) on synthetically useful timescales through base-assisted C‒H activation in nonpolar media at elevated temperature. Optimisation of the reaction conditions (various bases, solvents, methods) identified 1:2 mixtures of acetate and carbonate as unrivalled synergetic base pairs in the optimum protocol that holds promise as a readily usable and easily tuneable access to a wide range of direct nickelation products. While for the base-assisted C‒H metalation of the noble metals Ru, Ir, Rh, or Pd, this acetate/carbonate method has been established for a few years, our study represents the leap into the world of the base metals of the 3d series.

scholarly journals Oxidative Addition of Aryl Halides to a Ni(I)-Bipyridine Complex

2022 ◽  
Author(s):  
Stephen Ting ◽  
Wendy Williams ◽  
Abigail Doyle
Keyword(s):  
Oxidative Addition ◽  
Aryl Halides ◽  
Solution Phase ◽  
Nickel Catalysis ◽  
Mechanistic Studies ◽  
Redox Equilibrium ◽  
Aryl Bromides ◽  
First Time

The oxidative addition of aryl halides to bipyridine- or phenanthroline-ligated nickel(I) is a commonly proposed step in nickel catalysis. However, there is a scarcity of complexes of this type that both are well-defined and undergo oxidative addition with aryl halides, hampering organometallic studies of this process. We report the synthesis of a well-defined Ni(I) complex, [(CO2Etbpy)NiCl]4 (1). Its solution-phase speciation is characterized by a significant population of monomer and a redox equilibrium that can be perturbed by π-acceptors and σ-donors. 1 reacts readily with aryl bromides, and mechanistic studies are consistent with a mechanism proceeding through an initial Ni(I) → Ni(III) oxidative addition. Such a process was demonstrated stoichiometrically for the first time, affording a structurally characterized Ni(III) aryl complex.

scholarly journals The molecular chemistry of diffuse and translucent clouds in the line-of-sight to Sgr B2: Absorption by simple organic and inorganic molecules in the GBT PRIMOS survey

2018 ◽  
Vol 610 ◽  
pp. A10 ◽  
Author(s):  
J. F. Corby ◽  
B. A. McGuire ◽  
E. Herbst ◽  
A. J. Remijan
Keyword(s):  
Molecular Hydrogen ◽  
Galactic Center ◽  
Galactic Disk ◽  
Outer Edge ◽  
Line Of Sight ◽  
Galactocentric Distance ◽  
Molecular Chemistry ◽  
Inorganic Molecules ◽  
Diffuse Clouds ◽  
First Time

The 1–50 GHz PRebiotic Interstellar MOlecular Survey (PRIMOS) contains ~50 molecular absorption lines observed in clouds located in the line-of-sight to Sgr B2(N). The line-of-sight material is associated with diffuse and translucent clouds located in the Galactic center, bar, and spiral arms in the disk. We measured the column densities and estimate abundances, relative to H2, of 11 molecules and additional isotopologues observed in this material. We used absorption by optically thin transitions of c-C3H2 to estimate the molecular hydrogen columns, and argue that this method is preferable to more commonly used methods. We discuss the kinematic structure and abundance patterns of small molecules including the sulfur-bearing species CS, SO, CCS, H2CS, and HCS+; oxygen-bearing molecules OH, SiO, and H2CO; and simple hydrocarbon molecules c-C3H2, l-C3H, and l-C3H+. Finally, we discuss the implications of the observed chemistry for the structure of the gas and dust in the ISM. Highlighted results include the following. First, whereas gas in the disk has a molecular hydrogen fraction of 0.65, clouds on the outer edge of the Galactic bar and in or near the Galactic center have molecular fractions of 0.85 and >0.9, respectively. Second, we observe trends in isotope ratios with Galactocentric distance; while carbon and silicon show enhancement of the rare isotopes at low Galactocentric distances, sulfur exhibits no trend with Galactocentric distance. We also determine that the ratio of c-C3H2/c-H13CCCH provides a good estimate of the 12C/13C ratio, whereas H2CO/H213CO exhibits fractionation. Third, we report the presence of l-C3H+ in diffuse clouds for the first time. Finally, we suggest that CS has an enhanced abundance within higher density clumps of material in the disk, and therefore may be diagnostic of cloud conditions. If this holds, the diffuse clouds in the Galactic disk contain multiple embedded hyperdensities in a clumpy structure, and the density profile is not a simple function of AV.

Oxidative addition of Bi–C bonds to Pt(0): reaction of Pt(PEt3)3 with cyclic organobismuth compounds

2020 ◽  
Vol 56 (96) ◽  
pp. 15216-15219
Author(s):  
Shigeru Shimada ◽  
Xiang-Bo Wang ◽  
Masato Tanaka
Keyword(s):  
Transition Metal ◽  
Metal Complex ◽  
Transition Metal Complex ◽  
Oxidative Addition ◽  
First Time

Oxidative addition of a Bi–C bond to a transition metal complex was demonstrated for the first time.

Annulate lamellae in the Sertoli cells of guinea pig testis after unilateral torsion of the spermatic cord

1984 ◽  
Vol 42 ◽  
pp. 196-197
Author(s):  
J. Chakraborty ◽  
A. P. Sinha Hikim ◽  
J. S. Jhunjhunwala
Keyword(s):  
Sertoli Cells ◽  
Guinea Pigs ◽  
Spermatic Cord ◽  
Present Report ◽  
Cell Types ◽  
Annulate Lamellae ◽  
Spermatogenic Cells ◽  
Electron Microscopic ◽  
Structural Details ◽  
First Time

Although the presence of annulate lamellae was noted in many cell types, including the rat spermatogenic cells, this structure was never reported in the Sertoli cells of any rodent species. The present report is based on a part of our project on the effect of torsion of the spermatic cord to the contralateral testis. This paper describes for the first time, the fine structural details of the annulate lamellae in the Sertoli cells of damaged testis from guinea pigs.One side of the spermatic cord of each of six Hartly strain adult guinea pigs was surgically twisted (540°) under pentobarbital anesthesia (1). Four months after induction of torsion, animals were sacrificed, testes were excised and processed for the light and electron microscopic investigations. In the damaged testis, the majority of seminiferous tubule contained a layer of Sertoli cells with occasional spermatogonia (Fig. 1). Nuclei of these Sertoli cells were highly pleomorphic and contained small chromatinic clumps adjacent to the inner aspect of the nuclear envelope (Fig. 2).

Electron spectroscopic imaging and diffraction

1991 ◽  
Vol 49 ◽  
pp. 706-707
Author(s):  
M. Rühle ◽  
J. Mayer ◽  
J.C.H. Spence ◽  
J. Bihr ◽  
W. Probst ◽  
...  
Keyword(s):  
Materials Science ◽  
Electron Spectroscopic Imaging ◽  
Magnetic Filter ◽  
Magnetic Imaging ◽  
Illumination System ◽  
Probe Size ◽  
Diffraction Patterns ◽  
Fritz Haber ◽  
Koehler Illumination ◽  
First Time

A new Zeiss TEM with an imaging Omega filter is a fully digitized, side-entry, 120 kV TEM/STEM instrument for materials science. The machine possesses an Omega magnetic imaging energy filter (see Fig. 1) placed between the third and fourth projector lens. Lanio designed the filter and a prototype was built at the Fritz-Haber-Institut in Berlin, Germany. The imaging magnetic filter allows energy-filtered images or diffraction patterns to be recorded without scanning using efficient area detection. The energy dispersion at the exit slit (Fig. 1) results in ∼ 1.5 μm/eV which allows imaging with energy windows of ≤ 10 eV. The smallest probe size of the microscope is 1.6 nm and the Koehler illumination system is used for the first time in a TEM. Serial recording of EELS spectra with a resolution < 1 eV is possible. The digital control allows X,Y,Z coordinates and tilt settings to be stored and later recalled.

A Novel TEM Technique for Characterizing As-Grown CVD Diamond Films

1991 ◽  
Vol 49 ◽  
pp. 956-957 ◽  
Author(s):  
Z.L. Wang ◽  
J. Bentley ◽  
R.E. Clausing ◽  
L. Heatherly ◽  
L.L. Horton
Keyword(s):  
Diamond Films ◽  
Chemical Vapor ◽  
Growth Direction ◽  
Dark Field ◽  
Growth Surface ◽  
Specimen Preparation ◽  
Transmission Electron ◽  
Diffraction Patterns ◽  
First Time ◽  
Microstructural Studies

Microstructural studies by transmission electron microscopy (TEM) of diamond films grown by chemical vapor deposition (CVD) usually involve tedious specimen preparation. This process has been avoided with a technique that is described in this paper. For the first time, thick as-grown diamond films have been examined directly in a conventional TEM without thinning. With this technique, the important microstructures near the growth surface have been characterized. An as-grown diamond film was fractured on a plane containing the growth direction. It took about 5 min to prepare a sample. For TEM examination, the film was tilted about 30-45° (see Fig. 1). Microstructures of the diamond grains on the top edge of the growth face can be characterized directly by transmitted electron bright-field (BF) and dark-field (DF) images and diffraction patterns.

A microscopic marker experiment study on high temperature oxidation of Ni-Al alloy

1986 ◽  
Vol 44 ◽  
pp. 514-515
Author(s):  
Shou-kong Fan
Keyword(s):  
Transport Mechanism ◽  
High Temperature Oxidation ◽  
Transverse Section ◽  
Al Alloy ◽  
Metal Interface ◽  
Electron Microscopic ◽  
Temperature Oxidation ◽  
Analytical Electron ◽  
Microscopic Studies ◽  
First Time

Transmission and analytical electron microscopic studies of scale microstructures and microscopic marker experiments have been carried out in order to determine the transport mechanism in the oxidation of Ni-Al alloy. According to the classical theory, the oxidation of nickel takes place by transport of Ni cations across the scale forming new oxide at the scale/gas interface. Any markers deposited on the Ni surface are expected to remain at the scale/metal interface after oxidation. This investigation using TEM transverse section techniques and deposited microscopic markers shows a different result,which indicates that a considerable amount of oxygen was transported inward. This is the first time that such fine-scale markers have been coupled with high resolution characterization instruments such as TEM/STEM to provide detailed information about evolution of oxide scale microstructure.

Direct imaging of charge transfer

1996 ◽  
Vol 54 ◽  
pp. 680-681
Author(s):  
Yimei Zhu ◽  
J. Tafto
Keyword(s):  
Charge Transfer ◽  
Electron Diffraction ◽  
Scattering Amplitude ◽  
High Temperature Superconductors ◽  
Charge Carriers ◽  
Image Charge ◽  
Net Charge ◽  
Long Time ◽  
Electron Holes ◽  
First Time

The electron holes confined to the CuO2-plane are the charge carriers in high-temperature superconductors, and thus, the distribution of charge plays a key role in determining their superconducting properties. While it has been known for a long time that in principle, electron diffraction at low angles is very sensitive to charge transfer, we, for the first time, show that under a proper TEM imaging condition, it is possible to directly image charge in crystals with a large unit cell. We apply this new way of studying charge distribution to the technologically important Bi2Sr2Ca1Cu2O8+δ superconductors.Charged particles interact with the electrostatic potential, and thus, for small scattering angles, the incident particle sees a nuclei that is screened by the electron cloud. Hence, the scattering amplitude mainly is determined by the net charge of the ion. Comparing with the high Z neutral Bi atom, we note that the scattering amplitude of the hole or an electron is larger at small scattering angles. This is in stark contrast to the displacements which contribute negligibly to the electron diffraction pattern at small angles because of the short g-vectors.

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