1450-14-2Relevant articles and documents
Catalytic Silylation of Dinitrogen with a Dicobalt Complex
Siedschlag, Randall B.,Bernales, Varinia,Vogiatzis, Konstantinos D.,Planas, Nora,Clouston, Laura J.,Bill, Eckhard,Gagliardi, Laura,Lu, Connie C.
, p. 4638 - 4641 (2015)
A dicobalt complex catalyzes N2 silylation with Me3SiCl and KC8 under 1 atm N2 at ambient temperature. Tris(trimethylsilyl)amine is formed with an initial turnover rate of 1 N(TMS)3/min, ultimately reaching a turnover number of ～200. The dicobalt species features a metal-metal interaction, which we postulate is important to its function. Although N2 functionalization occurs at a single cobalt site, the second cobalt center modifies the electronics at the active site. Density functional calculations reveal that the Co-Co interaction evolves during the catalytic cycle: weakening upon N2 binding, breaking with silylation of the metal-bound N2 and reforming with expulsion of [N2(SiMe3)3]-.
Some Aspects of Chemistry of the N->Si Chelated Aryloxydihydrosilanes R(ArO)SiH2(R = Ph, ArO) and of the 2,2-Diaryloxytrisilane (Me3Si)2Si(OAr)2{ArO = 2,4,6-[(CH3)2NCH2]3C6H2O}
Ahdab, Aman Akkari-El,Rima, Ghassoub,Gornitzka, Heinz,Barrau, Jacques
, p. 94 - 105 (2002)
Reactions of the pentacoordinate aryldioxydihydrosilane Ph(Ar)SiH2 (1) with hydroxyl groups, carbonyl derivatives and PCl5 resulted in formation of new alcoxylated, phenoxylated and halogenated hydrosilanes Ph(ArO)(H)X (X = Cl, OR, OAr, OC(O)R), respectively. Treatment of the hexacoordinated (4+2) diaryloxydihydrosilane (ArO)2SiH2 (2) with N-chloro- or N-bromosuccinimide, trimethylsilyltriflate or iodine yielded the novel stable silicenium ion [(ArO)2(H)Si](1+)X(1-). Reactions of 2 with sulfur S8 and the transition metal complex Fe(CO)5 have resulted in the isolation of the new complexes (ArO)2Si = E [E = S, Fe(CO)4]. Decomposition modes of the tetracoordinate 2,2-diaryloxytrisilane (Me3Si)2Si(OAr)2 (3) on thermolysis and photolysis have also been studied; two pathways involving formation of the two silylenes (ArO)(Me3Si): and (ArO)2Si: have been identified by trapping experiments
L'electrosynthese, une voie simple d'acces aux di- et polysilanes
Biran, C.,Bordeau, M.,Pons, P.,Leger, M.-P.,Dunogues, J.
, p. C17 - C20 (1990)
Electrochemical reduction of chlorosilanes, at constant current intensity, in a single compartment cell fitted with a sacrificial aluminium anode, is a practical and convenient route to di-, tri-, and poly-silanes.
Ultrasound in organometallic chemistry. The effects of temperature, metal purity and power source on the ultrasound-promoted reaction between trimethylchlorosilane and lithium
Lickiss, Paul D.,Lucas, Ronan
, p. 25 - 28 (1993)
The temperature, lithium purity, and the source of ultrasound (bath or probe) all have significant effect on the ultrasound-promoted reaction between Me3SiCl and Li to give Me3SiSiMe3.
Multiple-bond metathesis mediated by sterically pressured uranium complexes
Castro-Rodriguez, Ingrid,Nakai, Hidetaka,Meyer, Karsten
, p. 2389 - 2392 (2006)
(Figure Presented) Completing a circle of reactions: Reaction of a U V-imido complex (2) with a π acid (e.g., CH3NC) affords a UIV-heterocumulene complex (3), which reacts with an alkyl halide to yield the free carbodiimide and corresponding UIV-halide complex (4). Reduction of complex 4 recovers 1, thereby closing a cycle in which a nitrogen atom is transferred from a UV-imido complex to a π acid by multiple-bond metathesis.
Molybdenum-catalyzed transformation of molecular dinitrogen into silylamine: Experimental and DFT study on the remarkable role of ferrocenyldiphosphine ligands
Tanaka, Hiromasa,Sasada, Akira,Kouno, Tomohisa,Yuki, Masahiro,Miyake, Yoshihiro,Nakanishi, Haruyuki,Nishibayashi, Yoshiaki,Yoshizawa, Kazunari
, p. 3498 - 3506 (2011)
A molybdenum-dinitrogen complex bearing two ancillary ferrocenyldiphosphine ligands, trans-[Mo(N2)2(depf)2] (depf = 1,1′-bis(diethylphosphino)ferrocene), catalyzes the conversion of molecular dinitrogen (N2) into silylamine (N(SiMe3) 3), which can be readily converted into NH3 by acid treatment. The conversion has been achieved in the presence of Me 3SiCl and Na at room temperature with a turnover number (TON) of 226 for the N(SiMe3)3 generation for 200 h. This TON is significantly improved relative to those ever reported by Hidai's group for mononuclear molybdenum complexes having monophosphine coligands [J. Am. Chem. Soc.1989, 111, 1939]. Density functional theory (DFT) calculations have been performed to figure out the mechanism of the catalytic N2 conversion. On the basis of some pieces of experimental information, SiMe3 radical is assumed to serve as an active species in the catalytic cycle. Calculated results also support that SiMe3 radical is capable of working as an active species. The formation of five-coordinate intermediates, in which one of the N2 ligands or one of the Mo-P bonds is dissociated, is essential in an early stage of the N2 conversion. The SiMe 3 addition to a "hydrazido(2-)" intermediate having the NN(SiMe3)2 group will give a "hydrazido(1-)" intermediate having the (Me3Si)NN(SiMe3)2 group rather than a pair of a nitrido (-N) intermediate and N(SiMe3) 3. The N(SiMe3)3 generation would not occur at the Mo center but proceed after the (Me3Si)NN(SiMe3) 2 group is released from the Mo center. The flexibility of the Mo-P bond between Mo and depf would play a vital role in the high catalysis of the Mo-Fe complex.
1: 2-Adducts from Silylenes and 1,3-butadiene
Bobbitt, Kevin L.,Gaspar, Peter P.
, p. 17 - 26 (1995)
Photochemical generation of dimethylsilylene, methyl(phenyl)silylene and diphenylsilylene in the presence of high concentrations of 1,3-butadiene leads to the formation of 1-sila-3,4-divinylcyclopentanes as major products in addition to the anticipated 1-silacyclopent-3- enes.Also obtained are the ene-reaction products from the silenes, formed by formal 1,3-silyl shifts in the bis(trimethylsilyl)arylsilanes that are employed as the photochemical precursors of MePhSi: and Ph2Si:.Evidence is presented that both the divinylsilacyclopentanes and the silacyclopent-3-enes arise from vinylsilirane intermediates that can be trapped by acetone, yielding stable 3,3-dimethyl-4-vinyl-1- sila-2-oxolanes.Keywords: Silicon; Silylene
Facile Synthesis of the Dicyanophosphide Anion via Electrochemical Activation of White Phosphorus: An Avenue to Organophosphorus Compounds
Liu, Liu Leo,Mei, Yanbo,Yan, Zeen
supporting information, p. 1517 - 1522 (2022/02/01)
Organophosphorus compounds (OPCs) have gained tremendous interest in the past decades due to their wide applications ranging from synthetic chemistry to materials and biological sciences. We describe herein a practical and versatile approach for the trans
Attenuation of Ni(0) Decomposition: Mechanistic Insights into AgF-Assisted Nickel-Mediated Silylation
Balakrishnan, Venkadesh,Chindan, Bincy,Murugesan, Vetrivelan,Rasappan, Ramesh
supporting information, p. 1438 - 1446 (2022/01/27)
In nickel-mediated Kumada cross-coupling reactions, low valent active nickel complexes are often generated in situ and the ligands usually govern the reactivity or stability of these complexes. However, the decomposition of active nickel complexes is inev
Method for preparing hexamethyl disilane
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Paragraph 0018-0037, (2019/07/04)
The invention discloses a method for preparing hexamethyl disilane. The method is characterized in that trimethylchlorosilane is treated as a raw material and reacts in a solvent under the effect of acomposite reducing agent, and NaX or KX is treated as a catalyst in the reaction; after reaction, the product is subject to post-treatment to obtain hexamethyl disilane; X is F, CI, Br, or I; the composite reducing agent is the combination of phosphorus and a metal reducing agent. According to the method, trimethylchlorosilane is treated as the raw material and is subject to reducing coupling reaction with the metal reducing agent and the nonmetallic phosphorus in the solvent. The hexamethyl disilane prepared according to the method has the advantages of being high in economic efficiency, high in yield, small in pollution, and simple to operate; the phosphorus is mixed with the metal reducing agent in the experiment, and the reaction condition is mild, and the safety is high; the yield isup to 85-95%.
