- Group 2 metal (Mg, Ca, Sr) silylamides supported by a cyclen-derived macrocyclic polyamine
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Heteroleptic bis(silyl)amides of magnesium and calcium [(L)M{N(SiMe3)2}] [M = Mg, Ca; LH = 1,4,7-trimethyl-1,4,7,10-tetraazacyclododecane; (Me3TACD)H] were previously synthesized from LH and [M{N(SiMe3)2}2]. Strontium bis(silyl)amides [Sr{N(SiMe3)2}2(thf)2] and [Sr{N(SiHMe2)2}2(thf)2/3] reacted with LH to give different types of products, depending on the presence of the β-SiH function. While the former underwent protonolysis to give the amido-bridged dimer [(L)Sr{N(SiMe3)2}]2 (1), the latter gave the adduct [(LH)Sr{N(SiHMe2)2}2] (2) as a stable solid. 2 slowly underwent an intramolecular Si-H/H-N dehydrocoupling in solution to give [{(L)SiMe2N(SiHMe2)}Sr{N(SiHMe2)2}] (3) by liberating H2. The results of transamination of 1 with HN(SiHMe2)2 depended on the relative stoichiometric ratio. A 1 : 1 mixture in n-pentane gave [{(L)SiMe2N(SiHMe2)}Sr{N(SiMe3)2}] (4) and H2, while excess HN(SiHMe2)2 gave the adduct 2 under similar conditions. Compounds 2 and 3 exhibit Sr? H-Si interactions according to X-ray crystallography, NMR, and IR spectroscopy. Lighter congeners of elusive [(L)Sr{N(SiHMe2)2}] were isolable for Mg (5) and Ca (6).
- Mukherjee, Debabrata,Shirase, Satoru,Beckerle, Klaus,Spaniol, Thomas P.,Mashima, Kazushi,Okuda, Jun
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- Yttrium and aluminium complexes bearing dithiodiolate ligands: Synthesis and application in cyclic ester polymerization
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Yttrium and aluminium complexes of two dithiodiolate ligands that feature different bridges (CF3)2C(OH)CH2SRSCH2C(OH)(CF3)2 (L1-H2, R = CH2CH2 and L2-H2, R = C6H4) were synthesized in good yields by reacting tris(silylamide)yttrium or trimethylaluminium with one equivalent of the proligand. All complexes were characterized by NMR and elemental analysis, and single-crystal X-ray structural analysis was also performed for one of the yttrium complexes. The catalytic activities of the four complexes in the ring-opening polymerization of ε-caprolactone and rac-lactide have been investigated. Furthermore, DOSY experiment and DFT calculations have been carried out to determine the structure of the isopropoxo derivative of the complex L2Y amide.
- Meduri,Cozzolino,Milione,Press,Sergeeva,Tedesco,Mazzeo,Lamberti
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- Emergence of a New [NNN] Pincer Ligand via Si?H Bond Activation and β-Hydride Abstraction at Tetravalent Cerium
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The cerium(IV) pyrazolate complexes [Ce(Me2pz)4]2 and [Ce(Me2pz)4(thf)] initiate β-hydride abstraction of the bis(dimethylsilyl)amido moiety, to afford a heteroleptic cerium(IV) species containing a dimethylpyrazolyl-substituted silylamido ligand, namely [Ce(Me2pz)3(bpsa)] (bpsa=bis((3,5-dimethylpyrazol-1-yl)dimethylsilyl)amido; Me2pz =3,5-dimethylpyrazolato), along with some cerium(III) species. Remarkably, the nucleophilic attack of the pyrazolyl at the silicon atom and concomitant Si?H-bond cleavage is restricted to the tetravalent cerium oxidation state and appears to proceed via the formation of a transient cerium(IV) hydride, which engages in immediate redox chemistry. When [Ce(Me2pz)4]2 is treated with [Li{N(SiMe3)2}], that is, in the absence of the SiH functionality, any redox chemistry did not occur. Instead, the ceric ate complex [LiCe2(Me2pz)9] and the stable mixed-ligand ceric species [Ce(Me2pz)2{N(SiMe3)2}2] were obtained.
- Anwander, Reiner,Bayer, Uwe,Sch?dle, Dorothea,Werner, Daniel
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- NOVEL TRISILYL AMINE DERIVATIVE, METHOD FOR PREPARING THE SAME AND SILICON-CONTAINING THIN FILM USING THE SAME
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Provided are a novel trisilyl amine derivative, a method for preparing the same, and a siliconcontaining thin film using the same, wherein the trisilyl amine derivative, which is a compound having thermal stability, high volatility, and high reactivity and being present in a liquid state at room temperature and under pressure where handling is possible, may form a high purity siliconcontaining thin film having excellent physical and electrical properties by various deposition methods.
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Paragraph 71; 72; 73
(2015/07/23)
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- Novel trisilyl amine derivative, method for manufacturing thereof and silicon-containing thin film use the same
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The present invention relates to a novel trisilyl amine derivative, a method for producing the same, and a thin film containing silicon produced by using the same. The trisilyl amine derivative of the present invention, which is a compound having thermal stability, high volatility, and high reactivity and being present in a liquid state at room temperature and under pressure where handling is possible, may form a high purity silicon-containing thin film having excellent physical and electrical properties by various deposition methods.COPYRIGHT KIPO 2015
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Paragraph 0063; 0064
(2016/12/07)
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- NOVEL AMINO-SILYL AMINE COMPOUND AND THE MANUFACTURING METHOD OF DIELECTRIC FILM CONTAINING SI-N BOND BY USING ATOMIC LAYER DEPOSITION
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Provided are a novel amino-silyl amine compound and a manufacturing method of a dielectric film containing Si-N bond using the same. Since the amino-silyl amine compound according to the present invention, which is a thermally stable and highly volatile compound, may be treated at room temperature and used as a liquid state compound at room temperature and pressure, the present invention provides a manufacturing method of a high purity dielectric film containing a Si-N bond even at a low temperature and plasma condition by using atomic layer deposition (PEALD).
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Paragraph 83; 84; 85; 86; 87; 88
(2016/01/01)
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- Synthesis and chemical properties of 1,3-dichloro-1,3-dihydridodisilazanes
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A trans-silylation route to 1,3-dichloro-1,3-dihydridodisilazanes, a novel class of polyfunctional disilazane, is described.Thus, heating hexamethyl- or heptamethyl-disilazane under reflux in the presence of an excess of dichlorohydrogenosilane R1SiHCl2, led to compounds of formula (R1ClHSi)2NR2 (R1=Me, Et, Vi or Ph and R2=H; R1=Me and R2=Me) in high yield.The exchange of chlorinated organosilicon moieties was strongly facilited by a catalytic amount of (n-Bu4N)F.Interpretation of the results and a few chemical properties of these novel disilazanes arereported.Key words: Silicon; Silazanes; Synthesis; Dichlorodisilazanes; Dihydridodisilazanes
- Bacque, Eric,Pillot, Jean-Paul,Birot, M.,Dunogues, J.,Bourgeois, G.,Petraud, M.
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p. 167 - 172
(2007/10/02)
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