1187680-47-2Relevant articles and documents
Carbene-dichlorosilylene stabilized phosphinidenes exhibiting strong intramolecular charge transfer transition
Roy, Sudipta,Stollberg, Peter,Herbst-Irmer, Regine,Stalke, Dietmar,Andrada, Diego M.,Frenking, Gernot,Roesky, Herbert W.
, p. 150 - 153 (2015)
The unstable species dichlorosilylene was previously stabilized by carbene. The lone pair of electrons on the silicon atom of (carbene)SiCl2 can form a coordinate bond with metal-carbonyls. Herein we report that (carbene)SiCl2 can stabilize a phosphinidene (Ar-P, a carbone analogue) with the general formula carbine→SiCl2→P-Ar (carbene = cyclic alkyl(amino) carbene (cAAC; 2) and N-heterocyclic carbene (NHC; 3)). Compounds 2 and 3 are stable, isolable, and storable at 0 °C (2) to room temperature (3) under an inert atmosphere. The crystals of 2 and 3 are dark blue and red, respectively. The intense blue color of 2 arises due to the strong intramolecular charge transfer (ICT) transition from πSi=P→ πcAAC. The electronic structure and bonding of 2, 3 were studied by theoretical calculations. The HOMO of the molecule is located on the πSi=P bond, while the LUMO is located at the carbene moiety (cAAC or NHC). The dramatic change in color of these compounds from red (3, NHC) to blue (2, cAAC) is ascribed to the difference in energy of the LUMO within the carbenes (cAAC/NHC) due to a lower lying LUMO of cAAC.
Lewis Acidity of Si6Cl12 and Its Role as Convenient SiCl2 Source
Tillmann, Jan,Moxter, Maximilian,Bolte, Michael,Lerner, Hans-Wolfram,Wagner, Matthias
, p. 9611 - 9618 (2015)
The free cyclohexasilane Si6Cl12 (1) was obtained in 66% yield from the corresponding Cl- diadduct [nBu4N]2[1·2Cl] and AlCl3 in C6H6. The substituted cyclohexasilane 1,1-(Cl3Si)2Si6Cl10 (2), however, cannot be liberated from [nBu4N]2[2·2Cl] under comparable reaction conditions. Instead, a mixture of several products was obtained, from which the oligosilane Si19Cl36 (3) crystallized in low yields. X-ray crystallography revealed 3 to consist of two Si5 rings, bridged by one silicon atom. Compound 1 possesses Lewis acidic sites above and below the ring centroid. Competition experiments reveal that their corresponding acid strengths are comparable to that of BCl3. The reaction of 1 with 6 equiv of 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (Idipp) leads to a complete breakdown of the cyclic scaffold and furnishes the dichlorosilylene adduct Idipp-SiCl2.
