Cuproussiloxane as two self-assemblies, CuOSiMeR and CuOSiMeR, with catalytic property.

Cuproussiloxane (1) was prepared from the reaction of silanediol R(Me)Si(OH) (R = N(SiMe)(2,6-PrCH)) and (CuMes) (Mes = 2,4,6-MeCH). The prepared compound crystalizes into two self-assemblies: CuOSiMeR ([(CuO)Si(Me)R], 1a) and CuOSiMeR ([(CuO)Si(Me)R], 1b). 1a and 1b feature dodecagonal and decagonal prism X-ray structures, respectively.

Homocoupling of Isocyanide at the Si(II) Center of Borylaminoamidinatosilylene.

Two borylaminoamidinatosilylenes (L)[(1,5-CH)B(Ar)N]Si (L = PhC(NtBu), Ar = 2,6-PrCH ()) and (L)[(1,5-CH)B(Ar')N]Si (Ar' = 2,4,6-MeCH ()) have been prepared and utilized to investigate the reaction toward isocyanide. Reactions of with the respective CN-2,6-MeCH and CNCy (Cy = -CH) produced compounds (L)Si(NAr)C(N-2,6-MeCH)B(1,5-CH)(CN-2,6-MeCH) () and (L)Si(NAr)C(NCy)C(NCy)B(1,5-CH)(CNCy) (). Reactions of with the respective CNCy and CN-2,6-MeCH yielded compounds -(L)SiN(Ar')C(NCy)B(1,5-CH)C(NCy) () and -(L)[(1,5-CH)B(Ar')N]SiC(CN-2,6-MeCH)N(2,6-MeCH)C(N-2,6-MeCH) ().

One- and Two-Electron Transfer Oxidation of 1,4-Disilabenzene with Formation of Stable Radical Cations and Dications.

Electron-transferable oxidants such as B(C F ) /nBuLi, B(C F ) /LiB(C F ) , B(C F ) /LiHBEt , Al(C F ) /(o-RC H )AlH (R=N(CMe CH ) CH ), B(C F ) /AlEt , Al(C F ) , Al(C F ) /nBuLi, Al(C F ) /AlMe , (CuC F ) , and Ag SO , respectively were employed for reactions with (L) Si C (SiMe ) (C SiMe ) (L=PhC(NtBu) , 1). The stable radical cation [1] was formed and paired with the anions [nBuB(C F ) ] (in 2), [B(C F ) ] (in 3), [HB(C F ) ] (in 4), [EtB(C F ) ] (in 5), {[(C F ) Al] (μ-F)] (in 6), [nBuAl(C F ) ] (in 7), and [Cu(C F ) ] (in 8), respectively. The stable dication [1] was also generated with the anions [EtB(C F ) ] (9) and [MeAl(C F ) ] (10), respectively.

One-Shot Synthesis and Melt Self-Assembly of Bottlebrush Copolymers with a Gradient Compositional Profile.

Morphological control plays a central role in soft materials design. Herein, we report the synthesis of a gradient bottlebrush architecture and its role in directing molecular packing in the solid state. Bottlebrush copolymers with gradient interfaces were prepared via one-shot ring-opening metathesis polymerization of - and -norbornene-capped macromonomers.

A Germylene/Borane Lewis Pair and the Remarkable C=O Bond Cleavage Reaction toward Isocyanate and Ketone Molecules.

A germylene/borane Lewis pair (2) was prepared from a 1,1-carboboration of amidinato phenylethynylgermylene (1) by B(C6 F5 )3 . Compound 2 reacted with iPrNCO and (4-MeOC6 H4 )C(O)Me, respectively, with cleavage of the C=O double bond. In the first instance, O and iPrNC insert separately into the Ge-B bond to yield a GeBC2 O-heterocycle (3) and a GeBC3 -heterocycle (4).

Folding-promoted TBACl-mediated chemo- and regioselective demethylations of methoxybenzene-based macrocyclic pentamers.

Tetrabutylammonium chloride (TBACl) salt alone has not been shown previously to be capable of removing methoxy groups. It is demonstrated here that the use of TBACl achieves efficient folding-promoted chemo- and regioselective demethylations, eliminating up to two out of five methyl groups situated in similar macrocyclic chemical microenvironments.