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1.
Sham K. Vasisht Gursharan Singh Pawan K. Verma 《Monatshefte für Chemie / Chemical Monthly》1986,117(2):177-183
Oxo-Mo(VI) imido-chloride, [MoOCl2(NH)(Et
2O)]
n
and nitrido-chloride, [Mo2O2Cl2(N)2(Et
2O)]
n
have been synthesized by equimolar reactions of MoOCl4 with HN(SiMe
3)2 and LiN(SiMe
3)2, respectively. Higher molar reactions of HN(SiMe
3)2 lead to imido-silylamido derivatives, [Mo2OCl3(NH)3(NHSiMe
3)]
n
, whereas those of LiN(SiMe
3)2 give silylimido bridged compounds, Mo4O4Cl4(NSiMe
3)6 and Mo4O4(NSiMe
3)8. Elemental analyses, redox titration, magnetic moment, molecular weight, molar conductance, infrared,1H-NMR and TG-DTG-DTA studies are reported.
Reaktionen von Bis(trimethylsilyl)amin und -amid mit MoOCl4
Zusammenfassung Durch equimolare Reaktionen von MoOCl4 mit HN(SiMe 3)2 und LiN(SiMe 3)2 wurden die Oxo-Mo(VI) Imido-chloride [MoOCl2(NH)(Et 2O)] n und die Nitrido-chloride [Mo2O2Cl2(N)2(Et 2O)] n dargestellt. Höhermolekulare Reaktionen von HN(SiMe 3)2 führen zu Imido-silylamido Derivaten [Mo2OCl3(NH)3(NHSiMe 3)] n , währenddessen die von LiN(SiMe 3)2 silylimidoüberbrückte Verbindungen ergeben: Mo4O4Cl4(NSiMe 3)6 und Mo4O4(NSiMe 3)8. Die Strukturen sind mit Elementaranalysen, Redoxtitrationen, Messung der magnetischen Momente, Molekulargewichten, molarer Leitfähigkeit, Infrarot,1H-NMR und TG-DTG-DTA-Untersuchungen charakterisiert.相似文献
2.
The series of ,-diiodopermethylpolysilanes, I(SiMe
2)
n
I, (n=4–6) andX(SiMe
2)4
X, (X=Cl, Br) has been prepared by the action of halogen on the corresponding cyclic compounds (SiMe
2)
n
. The mass spectra, NMR-, IR- andRaman-spectra of these compounds have been recorded.
Herrn Prof. Dr.Josef Schurz zum 60. Geburtstag gewidmet. 相似文献
3.
A series of mono-bipy and -phen complexes (bipy = bipyridine, phen = phenanthroline) of the perhalodisilanes, Si2F6, Si2Cl6 and Si2Br6, mixed methylhalodisilanes (Si2MenX6?n, X = Cl, I; n = 2,3) and Si3Cl8 · bipy have been prepared by reaction of the components, and have been characterized. complexes are obtained exclusively.The structures of all complexes involve coordination of the base to the more acidic silicon and perpendicular alignment of the SiSi axis on the plane of the ligand. This may be rationalised in terms of steric requirements of the different groups, the more demanding groups occupying the sterically more favorable positions vertical to the plane of the ligand. For Si3Cl8 · bipy, spectroscopic and chemical evidence suggests bipy-coordination to the center silicon. PMR investigations of the dissociation equilibria of the complexes in solution led to determination of the heats of formation of four of the complexes and to a qualitative estimation of the relative acceptor strengths of several disilanes. Contrary to expectation, silyl groups increase the acceptor strength of silicon considerably and in the order SiMe3 < SiMe2Cl < SiMeCl2 < SiCl3. The effect of a SiMe3, substituent group may be compared to that of Cl. Methylchlorosilyl groups may exceed the effect of Cl as indicated by the increase in acceptor strength in the sequence (R =) Me < Ci < SiMe2Cl < SiMeCl2 for the acceptor RSiCl2Me. Si3Cl8 is the strongest acceptor in the series. Assuming the structural suggestion for Si3Cl8 · bipy (center coordination) to be correct an increase in acceptor strength is indicated in the sequence SiCl3(Si2Cl5) < SiCl2(SiCl3)2 (Si = coordinating center). This may be interpreted mainly in terms of charge accepting capacity of the polarisable silyl groups. Another interesting sequence of acceptor strengths measured in this work is 1,1,2-Si2Me3F3, 1,2-Si2Me2F4 < Si2Me3Cl3 < 1,2-Si2Me2Cl4, showing fluorodisilanes to be weaker acceptors than chlorodisilanes. This result is compared to the heats of formation of SiX4 · 2py complexes. 相似文献
4.
Karl Hassler 《Monatshefte für Chemie / Chemical Monthly》1988,119(8-9):851-862
Trisilylphosphanes of the type PSi3
Me
x
Ph
9–x
are formed when sodium/potassiumphosphide reacts with methylphenylchlorosilanesMe
n
Ph
3–n
SiCl or with mixtures of methylphenylchlorosilanes. The phosphanes (SiMe
3)
n
P (SiMe
m
Ph
3–m
)3–n
(n, m=0, 1, 2, 3) were separated and purified by destillation or crystallization and their29Si as well as31P-NMR-spectra were recorded. 相似文献
5.
Infrared andRaman vibrational spectra ofn-Si4Cl10,n-Si5Cl12,neo-Si5Cl12 and [(SiCl3)3Si]2 have been measured and assigned. A local symmetry force field has been developed to simulate vibrational spectra of all (noncyclic) perchlorosilanes Si
n
Cl2n+2 known today (n=2, 3, 4, 5, 8). The observed spectra are reproduced satisfactorily
Die Vibrationsspektren linearer und verzweigter PerchlorsilaneSi n Cl 2n+2 und deren Simulierung mittels eines lokalen Symmetrie-Kraftfeldes
Zusammenfassung Infrarot- undRaman-Spektren vonn-Si4Cl10,n-Si5Cl12,neo-Si5Cl12 und [(SiCl3)3Si]2 wurden aufgenommen und zugeordnet. Ein lokales Symmetrie-Kraftfeld zur Simulation der Spektren aller bisher bekannten (nicht cyclischen) Perchlorsilane Si n Cl2n+2 (n=2, 3, 4, 5, 8) wird angegeben. Die beobachteten Spektren werden zufriedenstellend reproduziert相似文献
6.
K. Rossmanith 《Monatshefte für Chemie / Chemical Monthly》1966,97(5):1357-1364
Zusammenfassung Die wasserfr. Bromide der Lanthanide einschließlich LaBr3 und YBr3 wurden nach der Ammonbromid-Vakuummethode hergestellt und ihr Oxidbromidgehalt untersucht. Beim Europium entstand EuBr2, das bei Raumtemp. gegen Br2 stabil ist, in Gegenwart von Tetrahydrofuran (THF) jedoch leicht oxydiert wird. DieTHF-Verbindungen der Erdbromide wurden dargestellt; sie haben die ZusammensetzungMeBr3·4THF (Me=La, Ce, Pr),MeBr3·3,5THF (Me=Nd bis Er einschließlich Y) undMeBr3·3THF (Me=Tm, Yb, Lu). Die Löslichkeit inTHF wurde bestimmt. Durch die extraktive Überführung in dieTHF-Verbindungen können die Seltenerdbromide vom Oxidbromid vollständig befreit werden.
Mit 1 Abbildung 相似文献
The anhydrous bromides of the lanthanides including LaBr3 and YBr3 were prepared by the ammonium bromide-vacuummethod and their content of oxide bromide studied. For Europium there resulted EuBr2, which was stable against Br2 at room temperature, but was easily oxidised in the presence of tetrahydrofurane (THF). TheTHF-compounds of the rare earth bromides were prepared; their compositions areMeBr3·4THF (Me=La, Ce, Pr),MeBr3·3,5THF (Me=Nd to Er including Y) andMeBr3·3THF (Me=Tm, Yb, Lu). The solubility inTHF was determined. The rare earth bromides can be completely freed from oxide bromide by extractive convertion to theTHF-compounds.
Mit 1 Abbildung 相似文献
7.
Preparation, Structures, and EPR Spectra of the Rhenium(II) Thionitrosyl Complexes trans -[Re(NS)Cl3(MePh2P)2] and trans -[Re(NS)Br3(Me2PhP)2] The paramagnetic rhenium(II) thionitrosyl compounds trans-[Re(NS)Cl3(MePh2P)2] and trans-[Re(NS)Br3(Me2PhP)2] are characterized by crystal structure diffraction and EPR spectroscopy. Trans-[Re(NS)Cl3(MePh2P)2] is formed during the reduction of (a) [ReNCl2(MePh2P)3] with disulphur dichloride or (b) of mer-[ReCl3(MePh2P)3] with trithiazyl chloride. Trans-[Re(NS)Br3(Me2PhP)2] is the final product of the ligand exchange reaction of mer-[Re(NS)Cl2(Me2PhP)3] with bromine whereby the metal occurred to be simultaneusly oxidized. The crystal structure analyses show for trans-[Re(NS)Cl3(MePh2P)2] (monoclinic, C2/c, a = 13.831(3) Å, b = 13.970(1) Å, c = 14.682(2) Å, β = 95.33(1), Z = 4) and trans-[Re(NS)Br3(Me2PhP)2] (monoclinic, C2/c, a = 33.292(5) Å, b = 8.697(1) Å, c = 17.495(3) Å, β = 115.65(1), Z = 8) linear co-ordinated NS ligands (Re–N–S-angles 180° and 174.8°). The metal atom is octahedrally co-ordinated with the phosphine ligands in trans position to each other. X-band and Q-band EPR spectra of the rhenium(II) thionitrosyl complexes (5 d5 “low-spin” configuration, S = 1/2) are detected in the temperature range 295 ≥ T ≥ 130 K. They are characterized by well resolved 185,187Re hyperfine patterns. The hyperfine parameters are used to get information about the spin-density distribution of the unpaired electron in the complexes under study. 相似文献
8.
Alexander G. Sturm Tobias Santowski Julia I. Schweizer Dr. Lioba Meyer Dr. Kenrick M. Lewis Dr. Thorsten Felder Prof. Dr. Norbert Auner Prof. Dr. Max C. Holthausen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(36):8499-8502
The industrial production of monosilanes MenSiCl4−n (n=1–3) through the Müller–Rochow Direct Process generates disilanes MenSi2Cl6−n (n=2–6) as unwanted byproducts (“Direct Process Residue”, DPR) by the thousands of tons annually, large quantities of which are usually disposed of by incineration. Herein we report a surprisingly facile and highly effective protocol for conversion of the DPR: hydrogenation with complex metal hydrides followed by Si−Si bond cleavage with HCl/ether solutions gives (mostly bifunctional) monosilanes in excellent yields. Competing side reactions are efficiently suppressed by the appropriate choice of reaction conditions. 相似文献
9.
Preparation and Vibrational Spectra of Nonahalogenodirhodates(III), [Rh2ClnBr9-n]3?, n = 0–9 The pure nonahalogenodirhodates(III), A3[Rh2ClnBr9-n], A = K, Cs, (TBA); n = 0–4, 9, have been prepared. They are formed from the monomer chlorobromorhodates(III), [RhClnBr6-n]3?, n = 0–6, which are bridged to confacial bioctahedral complexes by ligand abstraction in less polar organic solvents. From the mixtures the complexions are separated by ion exchange chromatography on DEAE-cellulose. The solid, air-stable, air-stable, K-, Cs- and (TBA)-salts of [Rh2ClnBr9-n]3?, n = 0–4, are green, of [Rh2Cl9]3? are brown. The IR and Raman spectra of [Rh2Br9]3? and [Rh2Cl9]3? are assigned according to the point group D3h. The chlorobromodirhodates exist as mixtures of geometrical and structural isomers, which belong to different point groups. The vibrational spectra exhibit bands in characteristic regions; at high wavenumbers stretching vibrations with terminal ligands v(Rh—Clt): 360–320, v(Rh—Brt): 280–250; in a middle region with bridging ligands v(Rh—Clb): 300–270, v(Rh—Brb): 210–170 cm?1; the deformation bands are observed at distinct lower frequencies. The terminal ligands are fixed very strong, and the distance between v(Rh—Xt) and v(Rh—Xb) increases with decreasing size of the cations. 相似文献
10.
Sector-field mass spectrometry was used to probe the fragmentation patterns of the cationic silicon chlorides Si2Cln
+ (n = 1—6). For almost all Si2Cln
+ ions, Si—Si fragmentation predominates the Si—Cl bond cleavage both in the metastable ion and collisional activation mass spectra. Analysis of the fragmentation patterns indicates that the long-lived radical cation Si2Cl6
·+ corresponds to a complex [SiCl2·SiCl4]·+ rather than the intact molecular ion of hexachlorodisilane. The behavior of Si2Cl5
+ is consistent with the formation of the (trichlorosilyl)dichlorosilyl cation Cl3SiSICl2
+. Structural aspects are also discussed for the other Si2Cln
+ species. A semi-quantitative analysis of the fragmentation patterns in conjunction with the literature thermochemistry data was used to estimate some thermochemical properties of the Si2Cln
+ cations. 相似文献
11.
R. S. Lokhande S. A. Parab 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2009,83(5):771-774
Ion exchange equilibrium constant (K) for Cl−/Br− and Cl−/C2O42− system was studied at different temperatures from 30 to 45°C. For both uni-univalent and uni-bivalent exchange systems, the
value of K increases with rise in temperature i.e., from 1.16 at 30°C to 2.95 at 45°C for Cl−/Br− system and 19.5 at 30°C to 30.0 at 45°C for Cl−/C2O42− system indicating the endothermic ion exchange reaction. The difference in K values at the same temperature for the two was related to the ionic charge of exchangeable ions in the solution.
The article is published in the original. 相似文献
12.
The two compounds, Me4Si2 (C2H3)2 and Me8Si2 (C2H3)2 have been studied by the anti-symmetrized free electron molecular orbital method. Electron delocalisation over the whole chain via the silicon atoms occurs and a satisfactory account of the electronic spectra may be obtained.
We wish to thank the S.R.C. for a maintenance grant to one of us (D.R.A.). 相似文献
Zusammenfassung Me4Si2 (C2H3)2 und Me8Si4 (C2H3)2 wurden nach der MO-Methode des freien Elektronengases behandelt. Delokalisierung der Elektronen über die Si-Atome der Kette wird festgestellt. Die berechneten Spektren sind zufriedenstellend.
Résumé On a étudié par la méthode des orbitales moléculaires d'électrons libres avec antisymétrisation les composés Me4Si2(C2H3)2 et Me8Si4(C2H3)2. Il se produit une délocalisation électronique le long de toute la chaÎne par l'intermédiaire des atomes de silicium, et l'on peut rendre compte d'une manière satisfaisante des spectres électroniques.
We wish to thank the S.R.C. for a maintenance grant to one of us (D.R.A.). 相似文献
13.
David A. Burns Eric M. Press M. A. Siegler Rebekka S. Klausen V. Sara Thoi 《Angewandte Chemie (International ed. in English)》2020,59(2):763-768
We report the synthesis of a set of 2D metal–organic frameworks (MOFs) constructed with organosilicon‐based linkers. These oligosilyl MOFs feature linear SinMe2n(C6H4CO2H)2 ligands (lin‐Sin, n=2, 4) connected by Cu paddlewheels. The stacking arrangement of the 2D sheets is dictated by van der Waals interactions and is tunable by solvent exchange, leading to reversible structural transformations between many crystalline and amorphous phases. 相似文献
14.
α,ω-Dibromopermethyloligosilanes, Br(SiMe2)
n
Br (n=2–4, 6), were prepared by the reaction of dodecamethylcyclohexasilane with bromine. The reaction of (Me2Si)6 with MCl4 (M=Sn, Ti) proceeds with the cleavage of Si−Si- and Si−C-bonds with the formation of α,ω-dichloropermethyloligosilanes, Cl(SiMe2)
n
Cl (n=2–4, 6), and chloro derivatives of cyclohexasilane, Cl
m
Si6Me12−m
(m=1, 2). Silane-siloxane copolymers of regular structure were obtained by heterofunctional copolycondensation of α,ω-dihalopermethyloligosilanes
with 1,5-dihydroxyhexamethyltrisiloxane.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1513–1517, August, 1997. 相似文献
15.
A. A. Kamyshova A. Z. Kreindlin P. V. Petrovskii A. S. Peregudov Yu. A. Borisov A. A. Koridze 《Russian Chemical Bulletin》2005,54(12):2805-2812
The reaction of [Cp*2RuBr]+Br− with bromine in CH2Cl2 (CD2Cl2) in an inert atmosphere at room temperature produces the complexes [Cp*Ru(Br)C5Me4CH2Br]+Br3
− (syn conformer), [Cp*Ru(Br)C5Me3(CH2Br)2]+ (syn and anti conformers), and [Ru(Br)(C5Me4CH2Br)2]+ (syn conformer). All complexes were characterized by 1H and 13C NMR spectroscopy; the former complex, by elemental analysis. These complexes were also prepared by the reaction of [Cp*RuC5Me4CH2]+BF4
− with bromine in CH2Cl2.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2712–2718, December, 2005. 相似文献
16.
M. Sc. Benedikt Köstler Dr. Michael Bolte Dr. Hans-Wolfram Lerner Prof. Dr. Matthias Wagner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(58):14401-14404
SixGey alloys are emerging materials for modern semiconductor technology. Well-defined model systems of the bulk structures aid in understanding their intrinsic characteristics. Three such model clusters have now been realized in the form of the SixGey heteroadamantanes [0] , [1] , and [2] through selective one-pot syntheses starting from Me2GeCl2, Si2Cl6, and [nBu4N]Cl. Compound [0] contains six GeMe2 and four SiSiCl3 vertices, whereas one and two of the GeMe2 groups are replaced by SiCl2 moieties in compounds [1] and [2] , respectively. Chloride-ion-mediated rearrangement quantitatively converts [2] into [1] at room temperature and finally into [0] at 60 °C, which is not only remarkable in view of the rigidity of these cage structures but also sheds light on the assembly mechanism. 相似文献
17.
Uwe Herzog Uwe Böhme Gerd Rheinwald 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):281-286
The reactions of Me2MCl2 (M = Si, Ge, Sn), Si2Me4Cl2, Si2Me2Cl3, Si2Me2Cl4 and CH2(SiCl2Me)2, and suitable mixtures thereof, with H2S / NEt3 and Li2E (E = Se, Te) have been investigated and lead to a variety of new group 14 chalcogenide systems. 相似文献
18.
Syntheses, Vibrational Spectra, and Normal Coordinate Analysis of Halogenonitrosylruthenates [Ru(NO)ClnBr5–n]2–, n = 0–5, and the Crystal Structure of (CH2py2)[Ru(NO)ClBr4] By treatment of [Ru(NO)Cl5]2– with anhydrous HBr in dichloromethane a mixture of [Ru(NO)ClnBr5–n]2–, n = 0–5, is formed, from which individual complexes can be separated by ion exchange chromatography on diethylaminoethyl cellulose. The X-Ray structure determination on a single crystal of (CH2py2)[Ru(NO)ClBr4] (monoclinic, space group P21/c, a = 11.480(2), b = 10.175(4), c = 16.025(6) Å, β = 107.40(1)°, Z = 4) reveals, that the chlorine atom is trans positioned to the nitrosyl group. The low temperature IR and Raman spectra have been recorded of six complexes of the series (n-Bu4N)2[Ru(NO)ClnBr5–n], n = 0–5, and are assigned by normal coordinate analysis. A good agreement between observed and calculated frequencies is achieved. The valence force constants are fd(NO) = 13.86–13.93 und fd(RuN) = 5.43–5.49 mdyn/Å. 相似文献
19.
Tobias Santowski Alexander G. Sturm Dr. Kenrick M. Lewis Dr. Thorsten Felder Prof. Dr. Max C. Holthausen Prof. Dr. Norbert Auner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(15):3809-3815
The Müller–Rochow direct process (DP) for the large-scale production of methylchlorosilanes MenSiCl4−n (n=1–3) generates a disilane residue (MenSi2Cl6−n, n=1–6, DPR) in thousands of tons annually. This report is on methylchlorodisilane cleavage reactions with use of phosphonium chlorides as the cleavage catalysts and reaction partners to preferably obtain bifunctional monosilanes MexSiHyClz (x=2, y=z=1; x,y=1, z=2; x=z=1, y=2). Product formation is controlled by the reaction temperature, the amount of phosphonium chloride employed, the choice of substituents at the phosphorus atom, and optionally by the presence of hydrogen chloride, dissolved in ethers, in the reaction mixture. Replacement of chloro by hydrido substituents at the disilane backbone strongly increases the overall efficiency of disilane cleavage, which allows nearly quantitative silane monomer formation under comparably moderate conditions. This efficient workup of the DPR thus not only increases the economic value of the DP, but also minimizes environmental pollution. 相似文献
20.
František Březina 《Monatshefte für Chemie / Chemical Monthly》1979,110(2):343-349
Compounds [Co(H2
L]X
2(X=Cl, Br, I, NO3, ClO4), [Co(H2
L–Br2)]Br2, [Co(H2
L–Br2)·py
2]Br2 and [Co(H2
L)Cl]Cl2 were isolated. They were investigated by means of thermoanalysis, IR and VIS spectroscopy, magnetochemistry and molar conductivity. 相似文献