Journal Article10.1021/JA301042U
A stable two-coordinate acyclic silylene.
Andrey V. Protchenko,Krishna Hassomal Birjkumar,Deepak Dange,Andrew D. Schwarz,Dragoslav Vidovic,Cameron Jones,Nikolas Kaltsoyannis,Philip Mountford,Simon Aldridge +8 more
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TL;DR: Simple two-coordinate acyclic silylene species, SiR(2), can be synthesized which is stable in the solid state up to 130 °C and undergoes facile oxidative addition reactions with dihydrogen and with alkyl C-H bonds, thus demonstrating fundamental modes of reactivity more characteristic of transition metal systems.
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Abstract: Simple two-coordinate acyclic silylenes, SiR2, have hitherto been identified only as transient intermediates or thermally labile species. By making use of the strong σ-donor properties and high steric loading of the B(NDippCH)2 substituent (Dipp = 2,6-iPr2C6H3), an isolable monomeric species, Si{B(NDippCH)2}{N(SiMe3)Dipp}, can be synthesized which is stable in the solid state up to 130 °C. This silylene species undergoes facile oxidative addition reactions with dihydrogen (at sub-ambient temperatures) and with alkyl C–H bonds, consistent with a low singlet–triplet gap (103.9 kJ mol–1), thus demonstrating fundamental modes of reactivity more characteristic of transition metal systems.
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References
Reversible, Metal-Free Hydrogen Activation
TL;DR: The compound (C6H2Me3)2PH(C 6F4)BH(C6F5)2 (Me, methyl), which is derived through an unusual reaction involving dimesitylphosphine substitution at a para carbon of tris(pentafluorophenyl) borane, cleanly loses H2 at temperatures above 100°C.
1.9K
Main-group elements as transition metals
TL;DR: The last quarter of the twentieth century and the beginning decade of the twenty-first witnessed spectacular discoveries in the chemistry of the heavier main-group elements, which led to new structural and bonding insights as well as a gradually increasing realization that the science more resembles that of transition-metal complexes than that of their lighter main- group congeners.
1.3K
π-Bonding and the Lone Pair Effect in Multiple Bonds Involving Heavier Main Group Elements: Developments in the New Millennium
Roland Fischer,Philip P. Power +1 more
TL;DR: The key unifying feature of almost all molecules discussed in this review is that they are generally stabilized by the use of bulky substituents which block associative or various decomposition pathways.
987
Tetramesityldisilene, a stable compound containing a silicon-silicon double bond
TL;DR: Irradiation of 2,2-bis(2,4,6-trimethylphenyl)hexamethyltrisilane in hydrocarbon solution produces tetramesityldisilene, which can be isolated as a yellow-orange solid stable to room temperature and above in the absence of air.
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