Takako Muraoka

Ultrasound-Induced Emission Enhancement Based on Structure-Dependent Homo- and Heterochiral Aggregations of Chiral Binuclear Platinum Complexes

Instant and precise control of phosphorescent emission can be performed by ultrasound-induced gelation of organic liquids with chiral, clothespin-shaped trans-bis(salicylaldiminato)Pt(II) complexes, anti-1. Nonemissive solutions of racemic, short-linked anti-1a (n = 5) and optically pure, long-linked anti-1c (n = 7) in organic liquids are transformed immediately into stable phosphorescent gels upon brief irradiation of low-power ultrasound. Emission from the gels can be controlled by sonication time, linker length, and optical activity of the complexes. Several experimental results indicated that structure-dependent homo- and heterochiral aggregations and ultrasound-control of the aggregate morphology are key factors for emission enhancement.

Synthesis of a base-stabilized silanone-coordinated complex by oxygenation of a (silyl)(silylene)tungsten complex.

Base-stabilized silanone complex Cp*(OC)(2)W(SiMe(3)){O═SiMes(2)(DMAP)} (2) was synthesized by the reaction of (silyl)(silylene)tungsten complex Cp*(OC)(2)W(SiMe(3))(═SiMes(2)) (1) with 1 equiv of pyridine-N-oxide (PNO) in the presence of 4-(dimethylamino)pyridine (DMAP). Further oxygenation of 2 with 3 equiv of PNO at 80 °C resulted in the formation of a W-O-Si-O-Si framework to give disiloxanoxy complex Cp*(O)(2)W{OSiMes(2)(OSiMe(3))} (3). Complex 3 was also obtained by the direct reaction of complex 1 with 4 equiv of PNO at 80 °C.

Rhodium-mediated silylative cyclization of 1,6-heptadiynes

Abstract RhCl(PPh 3 ) 3 ) readily reacts with an equivalent mole of a hydrosilane to form the SiRhH species that plays an important role in the silylative cyclization of 1,6-heptadiynes to construct 1,2-dialkylidenecyclopentane derivatives.

Rhodium-catalyzed approach to mannich-type products using aldimine, α,β-unsaturated ester, and hydrosilaneElectronic supplementary information (ESI) available: experimental details. See http://www.rsc.org/suppdata/cc/b2/b202773a/

A rhodium-catalyzed method for the synthesis of β-amino esters was accomplished in a one-pot procedure from aldimine, α,β-unsaturated ester and hydrosilane.

Rhodium-catalyzed substitution of allylic carbonates with enoxysilanes

Abstract Substitution at the allylic position proceeds smoothly in rhodium-catalyzed reactions of allyl carbonates with enoxysilanes under almost neutral conditions to give γ,δ-unsaturated ketones in good to excellent yields.

Rhodium-catalyzed silylative carbocyclization on C60

Rhodium-catalyzed three component coupling of hepta-1,6-diyne, hydrosilane and C60 proceeded smoothly to give a fullerene derivative in good yield.