Reactions of dodecamethylcyclohexasilane and polydimethylsilane with metal chlorides

Advances in disilylation reactions to access cis/trans-1,2-disilylated and gem-disilylated alkenes

“…In comparison to reactions employing Cl(SiMe 2 ) 3 Cl as the dimethylsilylene source, the advantage of using Si 6 Me 12 23 lies in its ease of handling and high atomic economy. 151,152 In 2018, the Nagashima group investigated the palladium-catalyzed reaction of Si 6 Me 12 with alkynes using 1-isocyanoadamantane (AdNC) as the ligand (Scheme 17). 153 They successfully synthesized 1,4disila-2,5-cyclohexadiene 24 from the reaction of the unreactive Si 6 Me 12 with an alkyne.…”

From Macrocyclic Oligo-acetylenes to Aromatic Ring Carbo-mers

“…Cyclosilanes (SiR 2 ) n (R = t Bu, Me, ...; n ≥ 3) have long been known . While the [3]pericyclyne ring has so far escaped isolation, hexamethyltrisila[3]pericyclyne 42 (Figure ) was obtained by extrusion of dimethylsilylene from the hexasila precursor (the ring 2- carbo -mer of cyclohexasilane: see section 4.1.1), and the role of the silicon vertexes on homoconjugation was analyzed on the basis of photoelectron spectra .…”

Syntheses of Substituted 1,4-Disila-2,5-cyclohexadienes from Cyclic Hexasilane Si6Me12 and Alkynes via Successive Si–Si Bond Activation by Pd/Isocyanide Catalysts

“…Insertion of an alkyne into a Si–Si bond of octaethylcyclotetrasilane also was achieved using a palladium catalyst . However, neither alkynes nor isocyanides reacted with dodecamethylcyclohexasilane (Si 6 Me 12 ; 1 ), due to the lack of sufficient ring strain. ,, …”