The solid-state structures of a series bithiazole and thiophene oligomers, as well substituted pentacenes, are rationalized in terms "pitch roll" inclinations from an "ideal" cofacial pi-stack. Pitch translate adjacent molecules relative to one another the direction long molecular axis, whereas roll along short axis. Thus, moderately large pitch distortions preserve pi-pi interactions between molecules, translations greater than 2.5 A essentially destroy overlap molecules. familiar...

The largest known Dy–Mn complex is [DyIII6MnIII4MnIV2(H2shi)4(Hshi)2(shi)10] (H3shi salicylhydroxamic acid; see stereopicture). Dy ions are arranged in a nearly planar hexagonal ring and capped on opposite sides by MnIII2MnIV trimer. This mixed-metal topology provides new structure class for the examination of interesting magnetic phenomena individual molecules. chemistry large lanthanide clusters has long been focus coordination chemists due to unique properties conferred upon molecules...

This communication describes the synthesis of a family unusually stable palladium(IV) complexes containing two chelating 2-phenylpyridine ligands and benzoates. These undergo clean C−O bond-forming reductive elimination upon heating, mechanism this catalytically relevant process has been studied in detail. Solvent effects, crossover experiments, Eyring plots (which show ΔS⧧ −1.4 ± 1.9 4.2 1.4 CDCl3 DMSO, respectively), Hammett analysis shows ρ = −1.36 0.04 substitution para-benzoate...

This communication describes oxidatively induced Ar−CF3 bond-forming reductive elimination from new PdII complexes of general structure (L∼L)PdII(Ar)(CF3). The electrophilic fluorinating reagent N-fluoro-2,4,6-trimethylpyridinium triflate promotes these reactions in good to excellent yields. palladium(IV) intermediate (tBu-bpy)PdIV(CF3)(F)(OTf)(C6H4F) has been isolated, characterized, and demonstrated undergo high yielding coupling upon thermolysis. work provides an attractive conceptual...

Abstract Boron clusters are proposed as a new concept for the design of magnesium‐battery electrolytes that magnesium‐battery‐compatible, highly stable, and noncorrosive. A novel carborane‐based electrolyte incorporating an unprecedented magnesium‐centered complex anion is reported shown to perform well electrolyte. This finding opens approach towards whose likelihood meeting challenging targets very high.

Luminescent lanthanide(III)-based molecular scaffolds hold great promises for materials science and biological applications. Their fascinating photophysical properties enable spectral discrimination of emission bands that range from the visible to near-infrared (NIR) regions. In addition, their strong resistance photobleaching makes them suitable long duration or repeated experiments using a broad sources excitation including intense focalized systems such as lasers (e.g., confocal...

A series of oxoperoxovanadium(V) complexes (ligands: H3nta = nitrilotriacetic acid, H3heida N-(2-hydroxyethyl)iminodiacetic H2ada N-(2-amidomethyl)iminodiacetic Hbpg N,N-bis(2-pyridylmethyl)glycine, and tpa N,N,N-tris(2-pyridylmethyl)amine) were characterized as functional models for the vanadium haloperoxidase enzymes. The crystal structures K[VO(O2)Hheida], K[VO(O2)ada], [VO(O2)bpg], H[VO(O2)bpg]2(ClO4) obtained. These all possess a distorted pentagonal bipyramidal coordination sphere...

The reaction of [(bzq)Pd(OAc)]2 (bzq = benzo[h]quinoline) with "CF3+" reagents to afford the monomeric PdIV aquo complex (bzq)Pd(CF3)(OAc)2(OH2) is demonstrated. Heating this adduct at 60 °C for 12 h leads highly chemoselective aryl−CF3 bond-forming reductive elimination. rate and yield transformation are both significantly enhanced by addition Brønsted Lewis acidic additives. mechanism C−CF3 bond formation from has been studied, major pathway proposed involve pre-equilibrium acetate...

The chiral, nucleophilic catalyst TADMAP [1, 3-(2,2,2-triphenyl-1-acetoxyethyl)-4-(dimethylamino)pyridine] has been prepared from 3-lithio-4-(dimethylamino)pyridine (5) and triphenylacetaldehyde (3), followed by acylation resolution. catalyzes the carboxyl migration of oxazolyl, furanyl, benzofuranyl enol carbonates with good to excellent levels enantioselection. oxazole reactions are especially efficient used prepare chiral lactams (23) lactones (30) containing a quaternary asymmetric...

The unprecedented polymorphism of the non-steroidal anti-inflammatory drug (NSAID) flufenamic acid (FFA) is described here. Nine polymorphs were accessed through use polymer-induced heteronucleation (PIHn) and solid–solid transformation at low temperature. Structural elucidation six these forms, in addition to two previously known makes FFA indisputably octamorphic. Although structure least one other form remains elusive, occurrence most under crystallization condition PIHn illustrates that...

Thirteen new multicomponent crystals (cocrystals and salts) of an anticonvulsant drug gabapentin with various carboxylic acid coformers have been discovered using the reaction crystallization method (RCM). These forms are characterized by X-ray powder diffraction (XRPD), Raman infrared spectroscopy, differential scanning calorimetry (DSC). Crystal structures 3-hydroxybenzoic (3HBA) 1, 4-hydroxybenzoic (4HBA) 2, salicylic 3, 1-hydroxy-2-napthoic (1H2NA) 4, RS-mandelic 5 also determined. While...

The intramolecular Pd-catalyzed carboetherification of alkenes affords 2-indan-1-yltetrahydrofuran products in moderate to good yield with excellent levels diastereoselectivity. stereochemical outcome these reactions is dependent on the structure Pd catalyst. Use PCy3 or P[(4-MeO)C6H4]3 as ligand for leads syn-addition arene and oxygen atom across double bond, whereas use (±)-BINAP DPP-benzene that result from anti-addition. catalyst-induced change stereochemistry likely due a reaction...

Oscillators omitted: A self-assembled inclusion complex between a LnIII[12-metallacrown-4]23+ sandwich motif (green and bronze) [24-metallacrown-8] (purple) is stable in methanol. The YbIII has large quantum yield (0.89 %) luminescent lifetime (14 μs) methanol, which are attributed to the exclusion of high-energy oscillators from within 6.7 Å emitting ion by metallacrown topology.

This manuscript describes the design, synthesis, characterization, and reactivity studies of organometallic NiIII complexes general structure TpNiIII(R)(R1) (Tp = tris(pyrazolyl)borate). With appropriate selection R R1 ligands, are stable at room temperature can be characterized by cyclic voltammetry, EPR spectroscopy, X-ray crystallography. Upon heating, many these compounds undergo C(sp2)–C(sp2) or C(sp3)–C(sp2) bond-forming reactions that challenging lower oxidation states nickel.

Two polymorphic hydrogen peroxide solvates of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20; wurtzitane is an alternative name to iceane) were obtained using hydrated α-CL-20 as a guide. These novel H2 O2 have high crystallographic densities (1.96 and 2.03 g cm-3 , respectively), predicted detonation velocities/pressures (with one solvate performing better than ϵ-CL-20), sensitivity similar that ϵ-CL-20. The use materials guide will be important in the development other...

Barely bidentate: The adduct of dimethylamino naphthalene (proton sponge) and 9-BBN-NTf2 is activated by steric hinderance for intermolecular borylation (see scheme). A contrasting addition/elimination pathway favored when using monodentate triethylamine which gives the first observable borenium salt (9-BBN-NEt3+ Tf2N−) lacking any n- or π-donor substitutents. Detailed facts importance to specialist readers are published as "Supporting Information". Such documents peer-reviewed, but not...

An amide-derived <italic>N</italic>,<italic>N</italic>,<italic>N</italic>-Ru(<sc>ii</sc>) complex catalyzes the conversion of EtOH to 1-BuOH with high activity.

Two relaxation processes of the magnetization in an antiferromagnetically coupled Dy₂ metallacrown-based complex.

This report describes a detailed investigation of acetate-assisted C–H activation at PdIV centers supported by the tris(2-pyridyl)methane (Py3CH) ligand. Mechanistic information about this transformation has been obtained through following: (i) extensive one- and two-dimensional NMR analysis, (ii) reactivity studies series substituted analogues, (iii) isotope effect studies. These experiments all suggest that [(Py3CH)PdIV(biphenyl)Cl2]+ occurs via multistep process involving...

The bmpi (1,3-bis(6′-methyl-2′-pyridylimino)isoindoline) pincer Ru(II) hydride complex catalyzes base-free, acceptorless, and chemoselective dehydrogenation of alcohols with liberation dihydrogen under moderate (<120 °C) conditions. Primary diols are converted to ester lactone products high conversion efficiencies. catalyst system is remarkably selective for the oxidation secondary in presence primary alcohols.

This communication describes the activation of CO2 at Ru pincer complex (PNN)Ru(H)(CO) (PNN = 6-(di-tert-butylphosphinomethylene)-2-(N,N-diethylaminomethyl)-1,6-dihydropyridine). The reaction proceeds to completion within minutes room temperature form a C–C bond between ligand and electrophilic carbon atom CO2. characterization both kinetic thermodynamic products reversibility this formation are discussed.

An amide-derived N,N,N-Fe(II) complex catalyzes the hydroboration of alkenes at room temperature. Alkylation a remote site on ligand backbone was used as late-stage modification to provide more electrophilic determined by electrochemical studies. The alkylated variant, compared parent complex, olefin with an increased reaction rate and exhibits distinct regioselectivity for internal alkene hydroboration.

This paper describes the one-electron interconversions of isolable NiIII and NiIV complexes through their reactions with carbon-centered radicals (R•). First, model are shown to react alkyl aryl afford products. Preliminary mechanistic studies implicate a pathway involving direct addition radical center. is directly analogous known reactivity NiII R•, step that commonly implicated in catalysis. Second, NiIV–CH3 complex C–C bonds via proposed SH2-type mechanism. leveraged enable challenging...

The preparation and characterization of a series encapsulated-lanthanide 15-metallacrown-5 complexes are reported. Planar ligands such as picoline hydroxamic acid (picha) or nonplanar alpha-amino acids (e.g., glycine (glyha)) led to one-step syntheses metallacrowns in yields high 85%. reaction the appropriate with copper acetate (1)/(5) equiv gadolinium(III) europium(III) nitrates DMF water yielded crystals Gd(NO(3))(3)[15-MC(Cu(II)N(picha))-5], 1, Eu(NO(3))(3)[15-MC(Cu(II)N(picha))-5], 2,...