Hydrocarbons activate! Isolable β-diketiminato dicopper–nitrene complexes such as 1 derived from the reaction of [{(Cl2NN)Cu}2(μ-benzene)] and 1-adamantylazide are potent towards nitrene insertion into unactivated sp3-hybridized CH bonds. allows stoichiometric catalytic intermolecular amination hydrocarbons to give secondary amines (see scheme). Catalyst loadings low 0.05 mol % may be used. Detailed facts importance specialist readers published "Supporting Information". Such documents...

A reactive iron compound bound to nitrogen has been isolated in an unusually high oxidation state.

The air stable complex [(PNP)FeCl(2)] (1) (PNP = N[2-P(CHMe(2))(2)-4-methylphenyl](2)(-)), prepared from one-electron oxidation of [(PNP)FeCl] with ClCPh(3), displays an unexpected S 3/2 to 5/2 transition above 80 K as inferred by the dc SQUID magnetic susceptibility measurement. ac magnetization data, at zero field and between frequencies 10 1042 Hz, clearly reveal 1 have frequency dependence on out-of-phase signal thus being a single molecular magnet thermally activated barrier U(eff)...

Abstract The low‐temperature (<−35 °C) reduction of the trivalent uranium monoarene complex [{( Ad,Me ArO) 3 mes}U] ( 1 ), with potassium spheres in presence a slight excess 2.2.2‐cryptand, affords quantitative conversion into uranium(II) [K(2.2.2‐crypt)][(( mes)U] 1‐K ). molecular and electronic structure was established experimentally by single‐crystal X‐ray diffraction, variable‐temperature H NMR X‐band EPR spectroscopy, solution‐state solid‐state magnetism studies, optical absorption...

Abstract Complexes of iron in high oxidation states are captivating research subjects due to their pivotal role as active intermediates numerous catalytic processes. Structural and spectroscopic studies well-defined model complexes often provide evidence these intermediates. In addition the fundamental molecular electronic structure insights gained by complexes, reactivity also affects our understanding reaction mechanisms for small molecule bond-activation chemistry. Here, we report...

This paper explores three aspects of strategic uncertainty: its relation to risk, predictability behavior and subjective beliefs players.In a laboratory experiment we measure subjects' certainty equivalents for coordination games one lottery.Behavior in is related risk aversion, experience seeking, age.From the distribution estimate probabilities successful wide range games.For many games, success predictable with reasonable error rate.The best response observed close global-game...

The theory of global games has shown that coordination with multiple equilibria may have a unique equilibrium if certain parameters the payoff function are private information instead common knowledge. We report results an experiment designed to test predictions this theory. Comparing sessions and information, we observe only small differences in behavior. For subjects coordinate on threshold strategies deviate from game solution towards payoff-dominant equilibrium. thresholds closer than...

Sterically pressured mid- to high-valent uranium complexes with an aryloxide substituted triazacyclononane ligand scaffold, [(((R)ArO)3tacn)(3-)], were studied for carbon dioxide activation and transformation chemistry. The high valent uranium(V) imido species [(((R)ArO)3tacn)U(NR)] (R = (t)Bu, R' 2,4,6-trimethylphenyl (2-(t)Bu); R Ad, (2-Ad); phenyl (3-(t)Bu)) synthesized spectroscopically characterized. X-ray crystallography of the tert-butyl mesityl derivative, 2-(t)Bu , reveals...

High on nitride: Discrete iron nitride complexes stabilized by N-anchored tris(carbene) ligands have been synthesized (see picture). These high-valent FeIVN are stable at room temperature, which allows their full spectroscopic and—for the first time—crystallographic characterization. Supporting information for this article is available WWW under http://www.wiley-vch.de/contents/jc_2002/2008/z800600_s.pdf or from author. Please note: The publisher not responsible content functionality of any...

Financial markets and macroeconomic environments are often characterised by positive externalities. In these environments, transparency may reduce expected welfare: public announcements serve as focal points for higher‐order beliefs affect agents' behaviour more than justified their informational contents. Some scholars conclude that reducing signals' precision or entirely withholding information improve welfare. This article shows should always be provided with maximum but, under certain...

The low-valent U(III) complexes [((t-BuArO)3mes)U] and [((AdArO)3N)U] react with CO2 to form the bridging carbonate [{((t-BuArO)3mes)U}2(μ-κ2:κ2-CO3)] [{((AdArO)3N)U}2(μ-η1:κ2-CO3)]. Uranium(IV) oxo have been determined be intermediate in these transformations.

A photoisomerizable diarylethene-derived ligand, phen*, has been successfully introduced into a spin-crossover iron(II) complex, [Fe(H2B(pz)2)2phen*] (1; pz =1-pyrazolyl). ligand-based photocyclization (photocycloreversion) in 1 modifies the ligand field, which, turn, results highly efficient paramagnetic high-spin → diamagnetic low-spin (low-spin high-spin) transition at coordinated Fe(II) ion. The reversible photoswitching of spin states, and thus associated magnetic properties, performed...

After decades of vituperative debate over the classical or nonclassical structure 2-norbornyl cation, long-sought x-ray crystallographic proof bridged, geometry this prototype carbonium ion in solvated [C7H11](+)[Al2Br7](-) • CH2Br2 salt has finally been realized. This achievement required exceptional treatment. Crystals obtained by reacting norbornyl bromide with aluminum tribromide undergo a reversible order-disorder phase transition at 86 kelvin due to internal 6,1,2-hydride shifts cation...

Abstract A novel π‐extended “superhelicene” based on hexa‐peri‐hexabenzocoronenes (HBCs) has been synthesized by an efficient four‐step synthetic procedure starting from diphenyl ether. Comprehensive structural analysis of the helicene was performed NMR spectroscopy and mass spectrometry measurements together with X‐ray analysis. Physicochemical superhelicene suitable HBC references revealed it had outstanding fluorescent features quantum yields over 80 %.

The redox series [Irn(NHx)(PNP)] (n = II–IV, x 3–0; PNP N(CHCHPtBu2)2) was examined with respect to electron, proton, and hydrogen atom transfer steps. experimental computational results suggest that the IrIII imido species [Ir(NH)(PNP)] is not stable but undergoes disproportionation respective IrII amido IrIV nitrido species. N–H bond strengths are estimated upon reaction reagents rationalize this observation used discuss reactivity of these compounds toward E–H activation.

Abstract Synthetic studies on the redox chemistry of trivalent uranium monoarene complexes were undertaken with a complex derived from chelating tris(aryloxide)arene ligand ( Ad,Me ArO) 3 mes 3− . Cyclic voltammetry [{( mes}U III ] 1 ) revealed nearly reversible and chemically accessible reduction at −2.495 V vs. Fc/Fc + —the first electrochemical evidence for formally divalent complex. Chemical indicates that induces coordination isomerization to form uranium(IV) hydride, addition crown...

Low-temperature photolysis experiments (T = 10 K) on the tripodal azido complex [(BIMPN(Mes,Ad,Me))Co(II)(N3)] (1) were monitored by EPR spectroscopy and support formation of an exceedingly reactive, high-valent Co nitrido species [(BIMPN(Mes,Ad,Me))Co(IV)(N)] (2). Density functional theory calculations suggest a low-spin d(5), S 1/2, electronic configuration central cobalt ion in 2 and, thus, are line with formulation as genuine, Co(IV) nitride species. Although reactivity this precludes...

Magnetic bistability in single-molecule magnets (SMMs) is a potential basis for new types of nanoscale information storage material. The standard model thermally activated relaxation the magnetization SMMs based on occurrence single Orbach process. Here, we show that incorporating phosphorus atom into framework dysprosium metallocene [(CpiPr5)Dy(CpPEt4)]+[B(C6F5)4]- (CpiPr5 penta-isopropylcyclopentadienyl, CpPEt4 tetraethylphospholyl) leads to two distinct high-temperature processes, with...

The synthesis, characterization, and reactivity of a series cobalt terminal imido complexes supported by an N-anchored tripodal tris(carbene) chelate is described, including Co-supported singlet nitrene. Reaction the CoI precursor [(TIMMNmes)CoI](PF6) (TIMMNmes = tris-[2-(3-mesityl-imidazolin-2-ylidene)-methyl]amine) with p-methoxyphenyl azide yields CoIII imide [(TIMMNmes)CoIII(NAnisole)](PF6) (1). Treatment 1 equiv [FeCp2](PF6) at -35 °C affords formal CoIV complex...

Abstract The binary germanides M 12 Ge 17 and 4 9 (M  Na, K, Rb, Cs) the stannides Sn were identified by a combination of direct synthesis, thermogravimetric analysis, vibrational spectroscopy, X‐ray powder data single crystal structure analysis. E phases contain cluster anions [E ] 4− in ratio 1:2, forming hierarchical with at atomic positions hexagonal Laves phase MgZn 2 . Like phases, compounds are derivatives cubic Cr 3 Si but [Ge anions. analyses give strong evidence for existence...

The reaction of [((t-BuArO)3tacn)UIII] (1) with 4,4′-di-tert-butylbenzophenone affords a unique isolable U(IV) ketyl radical species [((t-BuArO)3tacn)UIV(OC•t-BuPh2)] (2) supported by XRD data, magnetization measurements, and DFT calculations. Isolation full characterization the corresponding diphenyl methoxide complex [((t-BuArO)3tacn)UIV(OCHt-BuPh2)] (3) is also presented. one-electron reduction benzophenone [((AdArO)3tacn)UIII] (4) leads to purple intermediate [((AdArO)3tacn)UIV(OC•Ph2)]...