The Schiff base compound 2,2′-{[(2-aminoethyl)imino]bis[2,1-ethanediyl-nitriloethylidyne]}bis-2-hydroxy-benzoic acid (H4L) as a proligand was prepared in situ. This has three potential coordination pockets which make it possible to accommodate from one metal ions allowing for the formation of mono-, di-, and trinuclear complexes. Reaction situ H4L with Dy(NO3)3·5H2O resulted mononuclear complex [Dy(H3L)2](NO3)·(EtOH)·8(H2O) (1), shows SMM behavior. In contrast, reaction Mn(ClO4)2·6H2O...

We report a ternary hybrid photocatalyst architecture with tailored interfaces that boost the utilization of solar energy for photochemical CO2 reduction by synergizing electron and heat flows in photocatalyst. The comprises cobalt phthalocyanine (CoPc) molecules assembled on multiwalled carbon nanotubes (CNTs) are decorated nearly monodispersed cadmium sulfide quantum dots (CdS QDs). CdS QDs absorb visible light generate electron-hole pairs. CNTs rapidly transfer photogenerated electrons...

Abstract We describe a systematic method for the preparation and spectroscopic characterization of CO 2 molecule coordinated to an activated bisphenoidal nickel(I) compound containing tetraazamacrocyclic ligand in gas phase. The resulting complex was then structurally characterized by using mass‐selected vibrational predissociation spectroscopy. results indicate that highly distorted is bound metal center η ‐C,O coordination mode, thus establishing efficient rational metal‐activated further...

The ruthenium-catalyzed hydroamidation of terminal alkynes has evolved to become a broadly applicable tool for the synthesis enamides and enimides. Depending on catalyst system employed, reaction leads chemo-, regio-, stereoselectively single diastereoisomer. Herein, we present comprehensive mechanistic study alkynes, which includes deuterium-labeling, in situ IR, NMR, ESI–MS experiments complemented by computational studies. results support involvement ruthenium–hydride ruthenium–vinylidene...

We address the formation of hydrogen bonded domains among cationic constituents ionic liquid (IL) 1-(3-hydroxypropyl)pyridinium tetrafluoroborate [HPPy][BF4 ] by means cryogenic ion vibrational predissociation spectroscopy cold (ca. 35 K) gas-phase cluster ions and quantum chemistry. Specifically, analysis OH stretching bands reveals a chain-like OH⋅⋅⋅OH⋅⋅⋅OH⋅⋅⋅BF4- binding motif involving three cations in quinary (HPPy+ )3 (BF4- )2 . Calculations show that this cooperative H-bond attraction...

We report the vibrational spectra of hydronium and methyl-ammonium ions captured in C3v binding pocket 18-crown-6 ether ionophore. Although NH stretching bands CH3NH3+ ion are consistent with harmonic expectations, OH H3O+ surprisingly broad, appearing as a diffuse background absorption little intensity modulation over 800 cm-1 an onset ∼400 below prediction. This structure persists even when only single group is present HD2O+ isotopologue, while OD region displays regular progression...

We address the competition between intermolecular forces underlying recent observation that ionic liquids (ILs) with a hydroxyl-functionalized cation can form domains attractive interactions nominally repulsive positively charged constituents. Here we show this behavior is present even in isolated ternary (HEMIm+)2NTf2– complex (HEMIm+ = 1-(2-hydroxyethyl)-3-methylimidazolium) cooled to about 35 K photodissociation mass spectrometer. Of three isomers by double resonance techniques, one...

Electrochemical reactions and their catalysis are important for energy environmental applications, such as carbon neutralization water purification. However, the synergy in electrocatalysis between CO2 utilization wastewater treatment has not been explored. In this study, we find that electrochemical reduction of chlorinated organic compounds 1,2-dichloroethane, trichloroethylene, tetrachloroethylene into ethylene aqueous media, which is a category challenging due to competition H2...

Redox transformations at metal oxide (MOx)/solution interfaces are broadly important, and oxygen atom transfer (OAT) is one of the simplest most fundamental examples such reactivity. OAT a two-electron process, well-known in gas/solid reactions catalysis. However, rarely directly observed oxide/water interfaces, whose redox typically proposed to occur one-electron steps. Reported here stoichiometric organic molecules with aqueous colloidal titanium dioxide iridium nanoparticles (TiO2 IrOx...

Supported iron carbide particles have long served as catalysts for CO hydrogenation (the Fischer–Tropsch synthesis, FTS) and continue to be attractive. Despite this, little is known about their chemistry. Reported here a colloidal FexC nanoparticle (NP) model system that allows direct observation of surface hydrogen CO, well quantification the H. Dodecylamine-capped NPs (DDA-FexC NPs) were synthesized through solution-phase carburization Fe form stable colloids in low-polarity organic...

Two AgI ions, deprotonated 1-methyl-thymine (1MT-H)− and 1,3-dideaza-adenine (DDA), self-assemble in methanolic solution to a cationic [(Ag)2(1MT-H)(DDA)]+ complex as identified by electrospray ionization mass spectrometry. Assignment of vibrational bands identification the silver coordination pattern arise from comparison one- two-color Infrared Multiple Photon Dissociation (IRMPD) spectra (1000–4000 cm−1) isolated trapped complexes calculated density functional theory. This approach...

Abstract Ruthenium(II) complexes [(η 6 ‐cymene)RuCl(apypm)]BPh 4 with bidentate 2‐amino‐4‐(2‐pyridinyl)pyrimidine (apypm) ligands catalyze the transfer hydrogenation of acetophenone. Their activities are strongly dependent on substituent pattern pyrimidine ring. Complexes bearing a primary amino group in 2‐position ring do not perform catalysis terms “bifunctional mechanism”, although they possess protic hydrogen atoms at moiety close proximity to metal site. Systems containing tertiary...

Formation of N–H and N–C bonds from functionalization N2 is a potential route to utilization this abundant resource. One the key challenges make products activation reactive enough undergo further reactions under mild conditions. This paper explores strategy "alkali control," where presence an alkali metal cation enables reduction conditions, then chelation uncovers highly species that can break benzylic C–H give new Fe–C bonds. The ability "turn on" pathway with 18-crown-6 demonstrated...

Abstract A rational catalyst development based on mechanistic and spectroscopic investigations led to the discovery of a new protocol for catalytic hydroamidation reactions that draws easily available ruthenium trichloride trihydrate (RuCl 3 ⋅3 H 2 O) as precursor instead previously employed, expensive bis(2‐methylallyl)(1,5‐cyclooctadiene)ruthenium(II). This practical easy‐to‐use dramatically improves synthetic applicability Ru‐catalyzed hydroamidations. The catalyst, generated in situ from...

The strong temperature dependence of the I(-)·(H2O)2 vibrational predissociation spectrum is traced to intracluster dissociation ion-bound water dimer into independent monomers that remain tethered ion. thermodynamics this process determined using van't Hoff analysis key features quantify relative populations H-bonded and molecules. enthalpy isolated thus observed be reduced by roughly a factor three upon attachment cause reduction explored with electronic structure calculations potential...

The combined experimental and theoretical approach for the gas liquid phases provides a quantitative understanding of competition between differently H-bonded charged constituents in liquids.

We describe an instrumental configuration for the structural characterization of fragment ions generated by collisional dissociation peptide in typical MS2 scheme widely used sequencing. Structures are determined comparing vibrational band patterns displayed cryogenically cooled with calculated spectra candidate isomers. These were obtained a linear action mode photodissociation weakly bound D2 molecules. This is accomplished interfacing Thermo Fisher Scientific Orbitrap Velos Pro to...

Abstract Pyridinylazolato (N–N′) ruthenium(II) complexes of the type [(N–N′)RuCl(PMe 3 ) ] have been obtained in high yields by treating corresponding functionalised azolylpyridines with [RuCl 2 (PMe 4 presence a base. 15 N NMR spectroscopy was used to elucidate electronic influence substituents attached azolyl ring. The findings are agreement slight differences bond lengths ruthenium complexes. Furthermore, nature azolate moiety modulates catalytic activity hydrogenation carbon dioxide...

The FeMoco of nitrogenase is an iron–sulfur cluster with exceptional bond-reducing abilities. ENDOR studies have suggested that E4, the state binds and reduces N2, contains bridging hydrides as part active-site iron-sulfide cluster. However, there are no examples any isolable a hydride, which would test feasibility such species. Here, we describe diiron sulfide hydride complex prepared using mild method involving C–S cleavage added thiolate. Its reactions substrates show can act base or...

Abstract A series of bimetallic silyl halido cuprates consisting the new tripodal silicon‐based metalloligand [κ 3 N ‐Si(3,5‐Me 2 pz) Mo(CO) ] − is presented (pz=pyrazolyl). This straightforwardly accessible by reacting ambidentate ligand tris(3,5‐dimethylpyrazolyl)silanide ({Si(3,5‐Me } ) with [Mo(CO) (η 6 ‐toluene)]. The compound features a fac ‐coordinated chelating and an outward pointing, “free” pyramidal donor, which easily for secondary coordination to other metal centers. Several...

Recent advances in the coupling of vibrational spectroscopy with mass spectrometry create new opportunities for structural characterization metabolites great sensitivity. Previous studies have demonstrated this scheme on 300 K ions using very high power free electron lasers fingerprint region infrared. Here we extend scope approach to a single investigator scale as well spectral range include OH stretching fundamentals. This is accomplished by detecting IR absorptions linear action regime...

The synthesis of 2-substituted pyridine-pyrimidine ligands and their complexation with arene ruthenium(II) chloride moieties is reported. Depending on the electronic steric influences ligand, catalysts undergo CH activation by roll-over cyclometalation. This process opens up route to catalytic transfer hydrogenation ketones isopropanol as hydrogen source under base-free mild conditions. Barriers related cyclometalation can be determined experimentally collision-induced dissociation ESI mass...

Abstract A bimetallic catalyst system is presented that enables the decarboxylative cross‐coupling of triflates with carboxylate salts at only 100 °C, which 70 °C lower than previous Cu/Pd‐based systems. The new protocol allows coupling a broad range aryl various substituted 2‐nitrobenzoates in good to excellent yields. key feature bidentate P,N‐ligand designed bridge Pd and Cu centres thereby facilitating rate‐determining transmetalation step. Mass spectrometry (ESI‐MS) studies support...

There is great interest in developing Mn water-splitting catalysts due to their low cost, abundance, and relevance the oxygen-evolving complex (OEC). Three ligands with highly donating pyridine alkoxide moieties, including 2-(pyridin-2-yl)propan-2-ol (pyalkH), 2,2'-(pyridine-2,6-diyl)bis(propan-2-ol) (py-dialkH2 ), 2-[(2,2'-bipyridin)-6-yl]propan-2-ol (bipy-alkH), have been screened for oxygen-evolution catalysis. Complexes ligand bipy-alkH were shown evolve O2 when driven by Oxone...