Spectroscopic observation of silylene-ether complexes

Photochemistry of Cyclic Trisilanes: “Spring‐Loaded” Precursors to Methylphenylsilylene

“…[15][16][17] The corresponding silylenes are evidently the exclusive transient photoproducts in low temperature matrixes, which has allowed them to be charac-terized by UV/Vis and IR spectroscopy [18][19][20][21] and a number of aspects of their reactivity to be studied under these conditions. [7,19,[22][23][24][25][26][27][28][29][30] The high selectivity toward silylene extrusion is maintained in solution at room temperature in the case of dodecamethylcyclohexasilane (1), which has allowed the simplest dialkylsilylene derivative, SiMe 2 , to be studied directly in solution by time-resolved spectroscopic methods. [31][32][33][34] With the phenylated trisilanes 2 a and 2 b, on the other hand, a second photochemical process-1,3-silyl migration into the aryl ring, forming a transient silene derivative (3 a,b)-competes quite significantly with extrusion of the central Si(R)Ph moiety (see Scheme 1).…”

On the Mechanism of the Disproportionation of Chlorinated Silanes under the Influence of Lewis Bases

“…The coordination of Lewis bases to silylene was confirmed experimentally [9,10]. The resulting stabilization can lead to sterically and electronically stable silylenes such as the silandiyl, where the silylene is stabilized by two neighbouring nitrogen centers.…”

Heavy Analogs of Carbenes: Silylenes, Germylenes, Stannylenes and Plumbylenes

“…84 The trapping of silylene (i -Pr 3 Si)(t-Bu 3 Si)Si • •, generated by photolysis of the silirene precursor, with Me 3 SiH resulted in the formation of the intermolecular Si-H insertion product (i -Pr 3 Si)(t-Bu 3 Si)Si(H)SiMe 3 along with the intramolecular C-H insertion byproduct (Scheme 4.25). 63 Insertion of the thermally generated Me 2 Si • • or Me(Ph)Si • • into the highly strained Si-Si bond of 1,2-disilacyclobutene derivative gave trisilacyclopentenes as ring enlargement products (Scheme 4.27). 63 Insertion of the thermally generated Me 2 Si • • or Me(Ph)Si • • into the highly strained Si-Si bond of 1,2-disilacyclobutene derivative gave trisilacyclopentenes as ring enlargement products (Scheme 4.27).…”