Altering the binding affinities of tetraruthenocycles for polycyclic aromatic hydrocarbons by post-assembly modification.

We developed a strategy for manipulating the binding strength of polycyclic aromatic hydrocarbons (PAHs) via covalent post-assembly modification (PAM) of tetranuclear ruthenium macrocycles containing s-tetrazine ligands. The macrocycles act as efficient receptors for various PAHs. Inverse electron demand Diels-Alder (IEDDA) reaction of the macrocycles was applied to reduce the binding ability significantly.

New Condensation Polymer Precursors Containing Consecutive Silicon Atoms-Decaisopropoxycyclopentasilane and Dodecaethoxyneopentasilane-And Their Sol⁻Gel Polymerization.

The sol-gel polymerization of alkoxysilanes is a convenient and widely used method for the synthesis of silicon polymers and silicon-organic composites. The development of new sol-gel precursors is very important for obtaining new types of sol-gel products. New condensation polymer precursors containing consecutive silicon atoms-decaisopropoxycyclopentasilane (CPS) and dodecaethoxyneopentasilane (NPS)-were synthesized for the preparation of polysilane-polysiloxane material. The CPS and NPS xerogels were prepared by the sol-gel polymerization of CPS and NPS under three reaction conditions (acidic, basic and neutral). The CPS and NPS xerogels were characterized using N2 physisorption measurements (Brunauer-Emmett-Teller; BET and Brunauer-Joyner-Halenda; BJH), solid-state CP/MAS (cross-polarization/magic angle spinning) NMRs (nuclear magnetic resonances), TEM, and SEM. Their porosity and morphology were strongly affected by the structure of the precursors, and partial oxidative cleavage of Si-Si bonds occurred during the sol-gel process. The new condensation polymer precursors are expected to expand the choice of approaches for new polysilane-polysiloxane.

Antiallergic activity profile in vitro RBL-2H3 and in vivo passive cutaneous anaphylaxis mouse model of new sila-substituted 1,3,4-oxadiazoles.

A new class of sila-substituted 1,3,4-oxadiazoles was synthesized and evaluated for antiallergic activity using RBL-2H3 as the in vitro model and the in vivo anaphylactic mouse model. We observed that compound 5c effectively suppressed DNP-HSA-induced mast cell degranulation, compared to carbon analogue 9, and also suppressed the expression of TNF-α mRNA and Akt phosphorylation in antigen-stimulated RBL-2H3 cells. We also studied the effect of 5c in an in vivo passive cutaneous anaphylaxis (PCA) mouse model. The suppression by 5c was more effective than that by diphenylhydramine (DPH), a typical anti-histamine drug.

Reactivities of chlorotrisylsilylenoid with ketones.

Chlorotrisylsilylenoid reacted with both acetophenone and benzil to give the corresponding 2,5-dioxasilolanes and silylethers, respectively.

Synthetic applications with use of a silica-supported alkyne metathesis catalyst.

A highly active and durable fumed silica-supported heterogeneous molybdenum(VI) catalyst was applied to ring closing alkyne metathesis and cyclooligomerization reactions to give high yields of metathesis products near room temperature conditions.

A Mo(VI) alkylidyne complex with polyhedral oligomeric silsesquioxane ligands: homogeneous analogue of a silica-supported alkyne metathesis catalyst.

A highly active alkyne metathesis catalyst is realized by replacing the amide ligands of a molybdenum(VI) trisamide alkylidyne complex with silanol groups from incompletely condensed POSS (polyhedral oligomeric silsesquioxane) ligands. This catalyst serves as an effective homogeneous mimic of an amorphous silica-supported catalyst. Reactivities of various catalytic mixtures are reported along with an X-ray structure of the aniline-coordinated amidodisiloxymolybdenum(VI) alkylidyne complex.

Syntheses and reactivities of stable halosilylenoids, (Tsi)X2SiLi (Tsi=C(SiMe3)3, X=Br, Cl).

Halosilylenoids, stable at room temperature (Tsi)X(2)SiLi (Tsi=C(SiMe(3))(3), X=Br, Cl), were synthesized from the reaction of TsiSiX(3) with lithium naphthalenide. Bromosilylenoid reacted with tBuOH and MeI both at -78 degrees C and at room temperature to give (Tsi)HSiBr(2) and (Tsi)MeSiBr(2), respectively, in high yields; this clearly shows its nucleophilicity. In the reaction of bromosilylenoid with methanol, 2-propanol, and 2,3-dimethyl-1,3-butadiene, the corresponding products, (Tsi)HSi(OMe)(2), (Tsi)HSi(OiPr)Br, and bromo(Tsi)silacyclopent-3-ene, were obtained in high yields; this demonstrates its amphiphilic property, as if bromosilylene would be trapped. Chlorosilylenoid also exhibited both nucleophilic and amphiphilic properties. The (29)Si chemical shifts for (Tsi)Br(2)SiLi, (Tsi)Br(2)SiK, and (Tsi)Cl(2)SiLi were 106, 70, and 87 ppm, respectively.