Bimodules in crossed products of von Neumann algebras

In this paper, we study bimodules over a von Neumann algebra M   in the context of an inclusion M⊆M_?αG$M\subseteq M{?}_{\alpha }G$, where G is a discrete group acting on a factor M by outer ?-automorphisms. We characterize the M  -bimodules X⊆M_?αG$X\subseteq M{?}_{\alpha }G$ that are closed in the Bures topology in terms of the subsets of G  . We show that this characterization also holds for w^?$w^{?}$-closed bimodules when G has the approximation property (AP  ), a class of groups that includes all amenable and weakly amenable ones. As an application, we prove a version of Mercer's extension theorem for certain w^?$w^{?}$-continuous surjective isometric maps on X.     

Convenient syntheses of ring-B-nor analogues of Ambrox® and amberketal via a novel ring contraction reaction

Manool is converted into ring-B-nor analogues of commercially important perfumery compounds via a novel ring-B-nor intermediate methylene ketone 9. Compound 9 is synthesised via the formation of an exocyclic bromonium ion and the concomitant ring contraction of the B-ring of a diterpene skeleton derived from manool. Oxidation and base treatment of the ring-contracted product result in dehydrohalogenation and decarboxylation to afford methylene ketone compound 9, which is then converted to ring-B-nor analogues of Ambrox® and amberketal.     

C−H Activation of Inert Arenes using a Photochemically Activated Guanidinato-Magnesium(I) Compound

UV irradiation of solutions of a guanidinate coordinated dimagnesium(I) compound, [{(Priso)Mg}₂] 3 (Priso=[(DipN)₂CNPrⁱ₂]⁻, Dip=2,6-diisopropylphenyl), in either benzene, toluene, the three isomers of xylene, or mesitylene, leads to facile activation of an aromatic C−H bond of the solvent in all cases, and formation of aryl/hydride bridged magnesium(II) products, [{(Priso)Mg}₂(μ-H)(μ-Ar)] 4 – 9 . In contrast to similar reactions reported for β-diketiminate coordinated counterparts of 3 , these C−H activations proceed with little regioselectivity, though they are considerably faster. Reaction of 3 with an excess of the pyridine, p-NC₅H₄Bu^t (py^But), gave [(Priso)Mg(py^ButH)(py^But)₂] 10 , presumably via reduction of the pyridine to yield a radical intermediate, [(Priso)Mg(py^But⋅)(py^But)₂] 11 , which then abstracts a proton from the reaction solvent or a reactant. DFT calculations suggest two possible pathways to the observed arene C−H activations. One of these involves photochemical cleavage of the Mg−Mg bond of 3 , generating magnesium(I) doublet radicals, (Priso)Mg⋅. These then doubly reduce the arene substrate to give “Birch-like” products, which subsequently rearrange via C−H activation of the arene. Circumstantial evidence for the photochemical generation of transient magnesium radical species includes the fact that irradiation of a cyclohexane solution of 3 leads to an intramolecular aliphatic C−H activation process and formation of an alkyl-bridged magnesium(II) species, [{Mg(μ-Priso^−H)}₂] 12 . Furthermore, irradiation of a 1 : 1 mixture of 3 and the β-diketiminato dimagnesium(I) compound, [{(^DipNacnac)Mg}₂] (^DipNacnac=[HC(MeCNDip)₂]⁻), effects a “scrambling” reaction, and the near quantitative formation of an unsymmetrical dimagnesium(I) compound, [(Priso)Mg−Mg(^DipNacnac)] 13 . Finally, the EPR spectrum (77 K) of a glassed solution of UV irradiated 3 is dominated by a broad featureless signal, indicating the presence of a doublet radical species.     

Synthesis and Single Crystal Structures of N-Substituted Benzamides and Their Chemoselective Selenation/Reduction Derivatives

A series of N-aryl-N-(2-oxo-2-arylethyl) benzamides and cinnamides has been prepared. The reaction of the benzamides with Woollins’ reagent, a highly efficient chemoselective selenation/reduction reagent, gave the corresponding N-aryl-N-(arylenethyl) benzoselenoamides in good yields. Five representative single crystal X-ray structures are discussed.     

Transient spectroscopic characterization of the ring‐opening reaction of tetrahydrochromeno[2,3‐dimethyl]indole

Tetrahydrochromeno is a structural variant of spiropyran that undergoes a reversible ring‐opening to generate a colored nitrophenolate intermediate. Earlier work confirmed this intermediate through trimethylsilyl cyanide trapping under continuous irradiation. We have performed transient absorption spectroscopy to further characterize the mechanism of the ring‐opening reaction. Excitation at 355 nm produced a transient species with an absorption maximum at 445 nm, which we assign to the nitrophenolate unit of the ring‐opened product. The transient absorption decays after ~970 ns with small optical density changes corresponding to a 0.15 quantum yield. Exposure to oxygen did not exhibit a significant deleterious effect on the photoisomerization of the chromeno dye. Time‐dependent density functional theory corroborated spectroscopic assignments of the starting chromeno and the putative ring‐opened intermediate. The excited state behavior of this system parallels the structurally similar oxazine system reported by Raymo and coworkers. The one significant difference is the longer lifetime of the photochemically generated intermediate from chromeno. Copyright © 2015 John Wiley & Sons, Ltd.     

The anxiolytic effects of midazolam during anticipation to pain revealed using fMRI

BACKGROUND AND PURPOSE: Functional neuroimaging can distinguish components of the pain experience associated with anticipation to pain from those associated with the experience of pain itself. Anticipation to pain is thought to increase the suffering of chronic pain patients. Inappropriate anxiety, of which anticipation is a component, is also a cause of disability. We present a pharmacological functional magnetic resonance imaging (fMRI) study in which we investigate the selective modulation by midazolam of brain activity associated with anticipation to pain compared to pain itself. METHODS: Eight right-handed male volunteers underwent fMRI combined with a thermal pain conditioning paradigm and midazolam (30 mug/kg) or saline administration on different occasions, with order randomized across volunteers. Volunteers learned to associate a colored light with either painful, hot stimulation or nonpainful, warm stimulation to the back of the left hand. RESULTS: Comparison of the period during thermal stimulation (pain-warm) revealed a network of brain activity commonly associated with noxious stimulation, including activities in the anterior cingulate cortex (ACC), the bilateral insular cortices (anterior and posterior), the thalamus, S1, the motor cortex, the brainstem, the prefrontal cortex and the cerebellum. Comparison of the periods preceding thermal stimulation (anticipation to pain-anticipation to warm) revealed activity principally in the ACC, the contralateral anterior insular cortex and the ipsilateral S2/posterior insula. Detected by a region-of-interest analysis, midazolam reduced the activity associated specifically with anticipation to pain while controlling for anticipation to warm. This was most significant in the contralateral anterior insula (P<.05). There were no significant drug effects on the activity associated with pain itself. CONCLUSION: In identifying a pharmacological effect on activity preceding but not during pain, we have successfully demonstrated an fMRI assay that can be used to study the action of anxiolytic agents in a relatively small cohort of humans.     

Platinum Complexes Containing Pyramidalized Germanium and Tin Dihalide Ligands Bound through σ,σ ME Multiple Bonds

We present the isolation of the first mononuclear dihalogermylene, and mono‐ and dinuclear stannylene complexes of transition metals. These exhibit exceptionally pyramidalized Group 14 centers. Additionally, removal of the halide substituents from the Ge/Sn atom was successfully performed in two ways, halide abstraction and reduction, leading to a variety of unusual structural motifs.     

Reversible,Photoinduced Activation of P4 by Low‐Coordinate Main Group Compounds

Two unique systems based on low‐coordinate main group elements that activate P₄ are shown to quantitatively release the phosphorus cage upon short exposure to UV light. This reactivity marks the first reversible reactivity of P₄, and the germanium system can be cycled 5 times without appreciable loss in activity. Theoretical calculations reveal that the LUMO is antibonding with respect to the main group element–phosphorus bonds and bonding with respect to reforming the P₄ tetrahedron, providing a rationale for this unprecedented activity, and suggesting that the process is tunable based on the substituents.     

Experimental and Computational Studies of a Multi‐Electron Donor–Acceptor Ligand Containing the Thiazolo[5,4‐d]thiazole Core and its Incorporation into a Metal–Organic Framework

A ligand containing the thiazolo[5,4‐d]thiazole (TzTz) core (acceptor) with terminal triarylamine moieties (donors), N,N′‐(thiazolo[5,4‐d]thiazole‐2,5‐diylbis(4,1‐phenylene))bis(N‐(pyridine‐4‐yl)pyridin‐4‐amine ( 1 ), was designed as a donor–acceptor system for incorporation into electronically active metal–organic frameworks (MOFs). The capacity for the ligand to undergo multiple sequential oxidation and reduction processes was examined using UV/Vis‐near‐infrared spectroelectrochemistry (UV/Vis‐NIR SEC) in combination with DFT calculations. The delocalized nature of the highest occupied molecular orbital (HOMO) was found to inhibit charge‐transfer interactions between the terminal triarylamine moieties upon oxidation, whereas radical species localized on the TzTz core were formed upon reduction. Conversion of 1 to diamagnetic 2+ and 4+ species resulted in marked changes in the emission spectra. Incorporation of this highly delocalized multi‐electron donor–acceptor ligand into a new two‐dimensional MOF, [Zn(NO₃)₂( 1 )] ( 2 ), resulted in an inhibition of the oxidation processes, but retention of the reduction capability of 1 . Changes in the electrochemistry of 1 upon integration into 2 are broadly consistent with the geometric and electronic constraints enforced by ligation.     

An Investigation of Photo‐ and Pressure‐Induced Effects in a Pair of Isostructural Two‐Dimensional Spin‐Crossover Framework Materials

Two new isostructural iron(II) spin‐crossover (SCO) framework (SCOF) materials of the type [Fe(dpms)₂(NCX)₂] (dpms=4,4′‐dipyridylmethyl sulfide; X=S ( SCOF‐6(S) ), X=Se ( SCOF‐6(Se) )) have been synthesized. The 2D framework materials consist of undulating and interpenetrated rhomboid (4,4) nets. SCOF‐6(S) displays an incomplete SCO transition with only approximately 30 % conversion of high‐spin (HS) to low‐spin iron(II) sites over the temperature range 300–4 K (T_1/2=75 K). In contrast, the NCSe^? analogue, SCOF‐6(Se) , displays a complete SCO transition (T_1/2=135 K). Photomagnetic characterizations reveal quantitative light‐ induced excited spin‐state trapping (LIESST) of metastable HS iron(II) sites at 10 K. The temperature at which the photoinduced stored information is erased is 58 and 50 K for SCOF‐6(S) and SCOF‐6(Se) , respectively. Variable‐pressure magnetic measurements were performed on SCOF‐6(S) , revealing that with increasing pressure both the T_1/2 value and the extent of spin conversion are increased; with pressures exceeding 5.2 kbar a complete thermal transition is achieved. This study confirms that kinetic trapping effects are responsible for hindering a complete thermally induced spin transition in SCOF‐6(S) at ambient pressure due to an interplay between close T_1/2 and T(LIESST) values.