2003-85-2Relevant academic research and scientific papers
Rare Earth and Main Group Metal Poly(hydrosilyl) Compounds
Lampland, Nicole L.,Pindwal, Aradhana,Yan, Kaking,Ellern, Arkady,Sadow, Aaron D.
, p. 4546 - 4557 (2017)
The potassium poly(hydrosilyl) compound KSi(SiHMe2)3, which contains three β-SiH groups, is synthesized by the reaction of Si(SiHMe2)4 and KOtBu. A single-crystal X-ray diffraction study reveals chains composed of head-to-tail KSi(SiHMe2)3 monomers. This potassium poly(hydrosilyl) anion reacts with divalent metal halide salts in THF to form the bis(silyl) compounds Mg{Si(SiHMe2)3}2THF2 (1·THF2), Ca{Si(SiHMe2)3}2THF3 (2·THF3), and Yb{Si(SiHMe2)3}2THF3 (3·THF3). A trivalent yttrium bis(silyl), as part of a KCl-containing polymeric chain, is supported by K?H-Si bridging interactions. The N donors pyridine (py) and dimethylaminopyridine (DMAP) readily substitute THF, giving tetrahedral magnesium and octahedral calcium silyl compounds. The one-bond silicon-hydrogen coupling constants (1JSiH), infrared stretching frequencies (νSiH), and solid-state structures of 2·py4 and 3·THF3 indicate classical two center-two electron bonding between the metal center and the silyl ligand, as well as terminal (nonbridging) Si-H bonds within the silyl ligands. The magnesium and calcium compounds readily react with the Lewis acids PhB(C6F5)2 and B(C6F5)3 to give hydridoborate salts, whereas {κ3-ToM}2Yb (5) (ToM = tris(4,4-dimethyl-2-oxazolinyl)phenyl borate) is formed by reaction of TlToM and 3·THF3.
The Synthesis of the First Spiropentasilane, Octamethylspiropentasilane
Boudjouk, Philip,Sooriyakumaran, Ratnasabapathy
, p. 777 - 778 (1984)
The action of lithium metal on tetrakis(dimethylbromosilyl)silane or tetrakis(dimethylchlorosilyl)silane in tetrahydrofuran produces the first spiropentasilane, a highly strained polysilane that undergoes efficient cleavage reactions with lithium aluminium hydride, methylmagnesium bromide, and phosphorus pentachloride.
The influence of ring strain on the formation of Si-H-Si stabilised oligosilanylsilyl cations
Müller, Thomas,Nimoth, Jelte P.
, p. 16509 - 16513 (2021/12/07)
Hydride transfer between Si(SiMe2H)4 (2) and [Ph3C][B(C6F5)4] in 3-fluorotoluene yields the intermolecularly silane-stabilised silylium ion [((HMe2Si)3SiSiMe2)2H]+ ([5]+), independently of the amount of [Ph3C][B(C6F5)4] (0.5, 1.0 or 2.0 equiv.) used. The cyclic silane-stabilised silylium ion [4]+ is not detected by NMR spectroscopy. This result demonstrates the influence of ring strain effects on the formation of intra- ([4]+) or intermolecularly ([5]+) Si-H-Si bridged silyl cations.
Base catalysed hydrogenation of methylbromooligosilanes with trialkylstannanes, identification of the first methylbromohydrogenoligosilanes
Herzog,Roewer
, p. 117 - 124 (2007/10/03)
The Lewis base catalysed hydrogenation of methylchlorooligsilanes with trialkylstannanes can also be applied to the hydrogenation of methylbromooligosilanes. In this way methylbromohydrogenoligosilanes were prepared for the first time. Methylbromotrisilanes with an > SiBrMe middle group (e.g. SiBrMe2-SiBrMe-SiBrMe2) are hydrogenated First at this silicon atom under formation of an > SiHMe group (e.g. SiBrMe2-SiHMe-SiBrMe2). Brominated silanes containing a quarternary Si(Si)4 unit (e.g. Si(SiBrMe2)4) do not react with trialkylstannanes.
Tetrakis(dimethylsilyl)silane and Its Application in Synthesis
Kulpinski, Piotr,Lickiss, Paul D.,Stanczyk, Wlodzimierz
, p. 21 - 24 (2007/10/02)
Treatment of (ClMe2Si)4Si with LiAlH4 gives tetrakis(dimethylsilyl)silane, (HMe2Si)4Si (1), in 95percent yield.The silane (1), containing four active silicon-hydrogen bonds is an efficient free radical reducing agent and can also serve, in the presence of
