Spectroscopic characterization of molybdenum dinitrogen complexes containing a combination of di- and triphosphine coligands: 31P NMR analysis of five-spin systems

The three molybdenum-N2 complexes [Mo(N2)(dpepp)(depe)] (1), [Mo(N2)(dpepp)(dppe)] (2), and [Mo(N2)(dpepp)(1,2-dppp)] (3), all of which contain a combination of a bi- and a tridentate phosphine ligand, were prepared and investigated by vibrational and (31)P NMR spectroscopy. As a tridentate ligand bis(2-diphenylphosphinoethyl)phenylphosphine (dpepp) has been employed. The three different bidentate ligands are 1,2-bis(diethylphosphino)ethane (depe), 1,2-bis(diphenylphosphino)ethane (dppe), and R-(+)-1,2-bis(diphenylphosphino)propane (1,2-dppp). N-N as well as metal-N vibrations of 1-3 are identified and interpreted in terms of the geometric and electronic structures of the complexes. (31)P NMR spectra are recorded and fully analyzed. Moreover, correlation spectroscopy (COSY)-45 measurements are performed to determine the relative signs of coupling constants. Special attention is directed to a detection of different isomers and their (31)P NMR, as well as vibrational spectroscopic properties. The implications of the results for the area of synthetic nitrogen fixation with phosphine complexes are discussed.     

A Chemical Proteomic Strategy Reveals Inhibitors of Lipoate Salvage in Bacteria and Parasites

The development of novel anti-infectives requires unprecedented strategies targeting pathways which are solely present in pathogens but absent in humans. Following this principle, we developed inhibitors of lipoic acid ( LA ) salvage, a crucial pathway for the survival of LA auxotrophic bacteria and parasites but non-essential in human cells. An LA -based probe was selectively transferred onto substrate proteins via lipoate protein ligase (LPL) in intact cells, and their binding sites were determined by mass spectrometry. Probe labeling served as a proxy of LPL activity, enabling in situ screenings for cell-permeable LPL inhibitors. Profiling a focused compound library revealed two substrate analogs ( LAMe and C3 ) as inhibitors, which were further validated by binding studies and co-crystallography. Importantly, LAMe exhibited low toxicity in human cells and achieved killing of Plasmodium falciparum in erythrocytes with an EC₅₀ value of 15 μM, making it the most effective LPL inhibitor reported to date.     

Phosphino-Phosphination Reactions: Frustrated Lewis Pair Reactivity of Phosphino-Phosphonium Cations with Alkynes

The phosphino-phosphonium cations of the form [R₃PPR′₂]⁺ are labile and provide access to the constituent Lewis acidic and Lewis basic fragments. This permits frustrated Lewis pair-type addition reactions to alkynes, affording unprecedented phosphino-phosphination reactions and giving cations of the form [cis-R₃PCHC(R′′)PR′₂]⁺. This reactivity is further adapted to prepare several examples of a rare class of dissymmetric cis-olefin-linked bidentate phosphines.     

Non-affine structural evolution of soft colloidal crystalline latex films under stretching as observed via synchrotron X-ray scattering

A polymer dispersion consisting of soft latex spheres with a diameter of 135 nm was used to produce a crystalline film with face-centered cubic (fcc) packing of the spheres. Different from conventional small-molecule and hard-sphere colloidal crystals, the crystalline latex film in the present case is soft (i.e., easily deformable). The structural evolution of this soft colloidal latex film under stretching was investigated by in-situ synchrotron ultra-small-angle X-ray scattering. The film exhibits polycrystalline scattering behavior corresponding to fcc structure. Stretching results not only in a large deformation of the crystallographic structure but also in considerable nonaffine deformation at high draw ratios. The unexpected nonaffine deformation was attributed to slippage between rows of particles and crystalline grain boundaries. The crystalline structure remains intact even at high deformation, suggesting that directional anisotropic colloidal crystallites can be easily produced.     

PLD-assisted VLS growth of aligned ferrite nanorods, nanowires, and nanobelts-synthesis, and properties

We report here a systematic synthesis and characterization of aligned alpha-Fe2O3 (hematite), epsilon-Fe2O3, and Fe3O4 (magnetite) nanorods, nanobelts, and nanowires on alumina substrates using a pulsed laser deposition (PLD) method. The presence of spherical gold catalyst particles at the tips of the nanostructures indicates selective growth via the vapor-liquid-solid (VLS) mechanism. Through a series of experiments, we have produced a primitive "phase diagram" for growing these structures based on several designed pressure and temperature parameters. Transmission electron microscopy (TEM) analysis has shown that the rods, wires, and belts are single-crystalline and grow along <111>m or <110>h directions. X-ray diffraction (XRD) measurements confirm phase and structural analysis. Superconducting quantum interference device (SQUID) measurements show that the iron oxide structures exhibit interesting magnetic behavior, particularly at room temperature. This work is the first known report of magnetite 1D nanostructure growth via the vapor-liquid-solid (VLS) mechanism without using a template, as well as the first known synthesis of long epsilon-Fe2O3 nanobelts and nanowires.     

Phosphonium-borate zwitterions, anionic phosphines, and dianionic phosphonium-dialkoxides via tetrahydrofuran ring-opening reactions

Sterically demanding secondary phosphines and phosphides react with (THF)B(C(6)F(5))(3) (THF = tetrahydrofuran) to give the THF ring-opened compounds [R(2)PHC(4)H(8)OB(C(6)F(5))(3)] and [Mes(2)PC(4)H(8)OB(C(6)F(5))(3)Li(THF)(2)] (Mes = C(6)H(2)Me-2,4,6). These reactions also occur consecutively to give the double THF ring-opened compounds [Mes(2)P(C(4)H(8)OB(C(6)F(5))(3))(2)][Li(THF)(4)] and [t-Bu(2)P(C(4)H(8)OB(C(6)F(5))(3))(2)Li].     

Ultrafast ring-closure reaction of photochromic indolylfulgimides studied with UV-pump-IR-probe spectroscopy

The ring-opening and ring-closure reactions of a photochromic indolylfulgimide are investigated with femtosecond vibrational spectroscopy. Spectral signatures due to excited-state decay and vibrational cooling are seen in the mid-IR region. For the ring-opening reaction triggered with visible pulses, a lifetime of the excited electronic state of 4 ps was obtained in polar solution. In a nonpolar solvent, this time constant is reduced to 2 ps. The ring-closure reaction induced with UV pulses displays an excited-state lifetime and thus a building of the photoproduct of roughly 0.5 ps. For all processes, the subsequent cooling occurs on a 15-ps time scale lasting up to approximately 50 ps. The time-resolved IR measurements do not support the existence of any long-living intermediate states.     

Influence of Process Parameters on the Reaction Kinetics of the Chromium‐Catalyzed Trimerization of Ethylene

In this paper we report the results of an extensive experimental kinetic study carried out on the novel ethylene trimerization catalyst system, comprising the chromium source [CrCl₃(thf)₃] (thf=tetrahydrofuran), a Ph₂P‐N(iPr)‐P(Ph)‐N(iPr)H (PNPNH) ligand (Ph=phenyl, iPr=isopropyl), and triethylaluminum (AlEt₃) as activator. It could be shown that the initial activity shows a first‐order dependency on the ethylene concentration. Also, a first‐order dependency was found for the catalyst concentration. The initial activity follows a typical Arrhenius behavior with an experimentally determined activation energy of 52.6 kJ mol^?1. At elevated temperatures (ca. 80 °C), a significant deactivation was observed, which can be tentatively traced back to a ligand rearrangement in the presence of AlEt₃. After a fast initial phase, a pronounced ‘kink’ in the ethylene‐uptake curve is observed, followed by a slow, almost linear, further increase of the total ethylene consumption. The catalyst composition, in particular the ligand/chromium and the cocatalyst/chromium molar ratio, has a strong impact on the catalytic performance of the trimerization of ethylene.     

Hydrosilylation of alkynes by Ni(CO)3-stabilized silicon(II) hydride

Not copy and paste: Although β-diketiminato ligands have been employed for the stabilization of Ge(II) and Sn(II) hydrides, the corresponding Si(II) hydride is not accessible. However, coordination of silicon(II) to a {Ni(CO)(3)} fragment allowed the isolation of the first Si(II) hydride metal complex 1. This complex was used for the first silicon(II)-based and Ni(0)-mediated, stereoselective hydrosilylation of alkynes. R = phenyl, tolyl.