Recent Developments in the Reactivity of Stable Disilynes

Abstract

Unsaturated main group 14 species have unique properties and reactivity compared with their organic analogues. The isolation of stable disilynes, one of the most recent and intriguing additions to the catalog of unsaturated main group species, has opened the way for further studies into the differences between organic molecules and their heavy analogues. Since the isolation of the first disilyne, the reactivity and properties of these species has been the subject of numerous studies. Herein, the recent developments and results pertaining to the reactivity of disilynes are discussed.

Silicon(i) chemistry: the NHC-stabilised silicon(i) halides Si2X2(Idipp)2(X = Br, I) and the disilicon(i)-iodido cation [Si2(I)(Idipp)2]+

“…This can probably be attributed to the severely limited access to this very reactive class of compounds, as revealed by the very low yield synthesis (6.1%) of the only presently known example Si 2 Cl 2 (Idipp) 2 ( 2-Cl ) upon the reduction of SiCl 4 (Idipp) with C 8 K. 2 a Compounds B can be viewed as bis(NHC) adducts of the disilynes Si 2 R 2 ( A , Chart 1 ), the chemistry of which has flourished since the isolation of the first thermally stable compounds in 2004. 12 The NHC-stabilised Si I halides B bear as their amidinato ( C , Chart 1 ) 13 or (phosphino)enamido-stabilised congeners ( D , Chart 1 ), 14 a reactive Si–Si single bond and a lone pair of electrons at each silicon atom, but contain beyond displaceable halide and NHC substituents, which offer additional dimensions of reactivity. 15 In the present work, an efficient synthesis of NHC-stabilised Si I halides Si 2 X 2 (Idipp) 2 ( 2-X , X = Cl, Br, I) is reported, facilitating the exploration of their reactivity.…”

Synthesis and Characterization of Diphosphenes Bearing Fused‐Ring Bulky Rind Groups

“…In 1981, discrete molecules containing highly reactive Si Si [1], Si C [2], and P P [3] double bonds were successfully isolated by introducing the concept of kinetic stabilization with bulky protecting groups. Thereafter, a large variety of unsaturated compounds of the main group elements heavier than the second row elements have been synthesized with the appropriate bulky substituents or ligands [4][5][6][7][8][9][10]. In recent years, many efforts have been directed toward studying the incorporation of multiple bonds of the heavier main group elements into carbon π -conjugated systems because of their potentially useful properties and unique functions [11][12][13][14][15][16][17], including oligomers and polymers comprising P E (E = C, P) and Si Si bonds, which might offer a way to new elemento-organic hybrid materials.…”

Silicon–silicon π single bond

“…The structural features and electronic properties of the silicon-silicon π single bond were revealed by X-ray crystallography, electron paramagnetic resonance (EPR), magnetic susceptibility, ultraviolet/visible (UV/Vis), 29 Si nuclear magnetic resonance (NMR), and theoretical calculations. On the basis of these results, we propose this bond as a member of silicon-silicon bonds such as single bonds, double bonds [10][11][12][13][14][15][16][17] , and triple bonds [18][19][20][21][22] .…”