- Common features in the crystal structures of the compounds bis(dimethylstibanyl)oxane and -sulfane, and the minerals valentinite and stibnite (grauspiessglanz)
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Bis(dimethylstibanyl)oxane (1) and -sulfane (2), the two simplest organoelement species with an Sb-E-Sb fragment (E = O, S), were prepared by alkaline hydrolysis of bromodimethylstibane and by oxidation of tetramethyldistibane with sulfur [18], respectively. As shown by an x-ray structure analysis of compound 1 (m.p. 1,2121, a = 675.9(2), b = 803.1(2), c = 1666.8(4) pm at -70 ± 2°C; Z = 4; R1 = 0.042), the molecules (O-Sb 198.8 and 209.9 pm, Sb-O-Sb 123.0°) adopt a syn-anti conformation in the solid state and are arranged in zigzag chains along [010] via weak intermolecular O··Sb interactions (258.5 pm, Sb-O··Sb 117.8°, O··Sb-O 173.5°) making use, however, of only one Me2Sb moiety. Primary and secondary bond lengths and angles agree very well with corresponding values published for valentinite, the orthorhombic modification of antimony(III) oxide [3]. Bis(dimethylstibanyl)sulfane (2) (m.p. 29 to 31 °C) crystallizes in the uncommon space group P6522 (a = 927.8(3), c= 1940.9(7) pm at -100 ± 2°C; Z = 6; R1 =0.021). Owing to coordination numbers of (1 + 1) and (2 + 2) for both Me2Sb groups and the sulfur atom, respectively, molecules with an approximate syn-syn conformation (S-Sb 249.8 pm, Sb-S-Sb 92.35°) build up a three-dimensional net of double helices which are linked together by Sb · · S contacts (316.4 pm). These parameters shed more light onto the rather complicated structure and bonding situation in stibnite (antimony(III) sulfide [4]). The molecular packing of compound 2 is compared with the structures of relevant inorganic solids, especially with that of ss-quartz [37].
- Breunig,Lork,Roesler,Becker,Mundt,Schwarz
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Read Online
- Tetracarbonyl chromium complexes with Me2SbESbMe2 (E = O, S) and MeSb(SSbMe2)2 as ligands
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Me2SbOSbMe2 reacts with nbdCr(CO)4 (nbd = norbornadiene) to form cyclo-[Me2SbOSbMe2Cr(CO)4]2 (1). The reaction of Me2SbSSbMe2 with nbdCr(CO)4 gives cis-[(Me2SbSSbMe2)2Cr(CO)4] ( 2), a complex stable only in solution. With excess nbdCr(CO)4 also cyclo-[Me2SbSSbMe2Cr(CO)4]2 (3) and cyclo-[MeSb(SSbMe2)2Cr(CO)4] (4) form in low yield. The crystal structures of 1, 3 and 4 · nbdCr(CO)4 are reported. The novel ligand MeSb(SSbMe2)2 is formed by elimination of Me3Sb from Me2SbSSbMe2.
- Breunig,Joensson,Roesler,Lork
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p. 2120 - 2124
(2008/10/08)
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- Reactions of certain antimony(III, V) methyl derivatives with aliphatic alcohols in the presence of copper(II)
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Trimethylantimony and copper diacetate (or copper dipelargonate) in a 1:2 molar ratio substitute the hydrogen atom of the hydroxy group in aliphatic alcohols to form methyl alkyl ethers (yield up to 46%). The activity of alcohols toward methylation depends on the structure of the organic radical of the alcohol. Reactions of trimethylantimony diacetate or dibenzoate with alcohols in the presence of catalytic amounts of copper yield methyl alkyl ethers in 10-12% yields.
- Usyatinskii,Gushchin,Dodonov
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p. 1109 - 1112
(2007/10/03)
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- A trinuclear organoantimony cation: Structure of [Me2Sb- Sb(Me2)- SbMe2][Me2SbBr2]
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Only stable in the crystal, the title compound 1 contains the first example of a polynuclear organoantimony cation. Interionic Sb···Sb and Sb···Br contacts are observed in 1, and reversible dissociation of 1 in solution gives the starting materials Mc2ShBr and Mc4Sb2. These components exchange Mc2Sb groups in the formation of 1.
- Breunig,Denker,Lork
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p. 1005 - 1006
(2008/10/09)
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- The assessment of some Sb-Te single-source compounds for MOCVD applications
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The new compounds Et2SbTeEt, Me2SbTeEt, Et2SbTeiPr and Et2AsTeEt have been prepared by reactions of Et4Sb2, Me4Sb2 or Et4As2 with iPr2Te2 or Et2Te2.An alternative route to Et2SbTeEt involved the reaction of Et2SbBr with EtTeLi.The compounds are light sensitive, and some of them cannot be obtained pure because of facile radical decomposition or reverse dissociation to the corresponding R4E2 and R'2Te2.Thermal degradation of Et2SbTeEt in a hydrogen stream under conventional MOCVD condition gives a metal deposit containing Sb and Te in the ratio 1.6:1.The related compound Et2SbTeSbEt2 reacts with H2 at room temperature to give Te metal and presumably HSbEt2. Keywords: Antimony; Arsenic; Tellurium; MOCVD
- Dickson, Ron S.,Heazle, Kerryn D.
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p. 189 - 198
(2007/10/02)
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- Structuren von 2, MeSbI2, und I. Darstellung von Me3SbI2 und Farbwechsel bei Me4Sb2*Me2SbBr
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The crystal structures of the complex 2 (1) and its precursors MeSbI2 (2) and I (3) are reported.In 1 there are tetrahedral cations and square pyramidal anions with Sb-1 distances of 290-320 pm.The structure of 2 contains MeSbI2 molecules.They associate via iodine bridges to form linear chains with alternating short and long Sb-1 distances.The coordination around antimony is distorted tetragonal pyramidal.The tetrahedral coordination of the ions in 3 results in the formation of a wurtzite type structure with antimony-iodine distances of 406 and 435 pm.The novel adducts Me3Sb*MeSbI2 (4) and Me2SbSbMe2*Me2SbBr (5) are formed by reaction of the components.They decompose easily with formation of antimony(V) compounds.Crystals of 5 are yellow but become reversibly black on cooling.
- Breunig, Hans Joachim,Ebert, Klaus H.,Guelec, Sabahittin,Draeger, Martin,Sowerby, D. Bryan,et al.
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- Molecular Motion in Solid X, X = Cl, Br, I, PF6, and BF4. 1H, 19F NMR Second Moment and Crystal Structure
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The tumbling motion of the tetramethylstibonium cation (+) has been studied in the ionic compounds X, X = Cl, Br, I, PF6, and BF4, by measurement of the second moment of the protons M2(1H) in the temperature range 95 I was determined by single crystal X-ray diffraction: a = 728.4(3) pm, c = 1037.7(5) pm, space group C6v4-P63mc, Z = 2. - M2(1H) of I shows cation tumbling at T > 320 K.The methyl groups are rotating about their threefold axes in the whole temperature range studied. - In PF6 and BF4 both, cation and anion are tumbling at T >/= 259 K and T >/= 248 K, respectively, as seen by M2(1H) and M2(19F).A jump in the second moments and differential thermal analysis (DTA) of BF4 reveals a solid-solid phase transition with hysteresis (width 28 K).Activation energies for the tumbling motion of the tetramethylstibonium cation have been determined. - Complex Compounds / Crystal Structure / Molecular Dynamics / Phase Transitions / Spectroscopy, Nuclear Magnetic Resonance
- Burbach, Guenter,Dou, Shi-Qi,Weiss, Alarich
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p. 1302 - 1309
(2007/10/02)
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- Preparation of Dichalcogenostibanes of the Type RSb(ER')2 (R = CH3, C2H5; E = S, Se; R' = CH3, C6H5)
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Dichalcogenostibanes of the type RSb(ER')2 (R = CH3, C2H5; E = S, Se; R' = CH3, C6H5) and trialkylstibanes R3Sb have been prepared by redistribution reactions of stibanes of the type R2SbER'. - Keywords: Alkyldi(organochalcogeno)stibanes, Redistribution Reactions of Dialkyl(organochalcogeno)stibanes, 1H NMR Spectra, Raman Spectra, Mass Spectra
- Breunig, Hans Joachim,Guelec, Sabahittin
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p. 998 - 1002
(2007/10/02)
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- SPALTUNG VON TETRAMETHYLDISTIBAN MIT BROM, IOD UND METHYLIODID. BILDUNG DES ADDUKTS MeSbI2*2Me4SbI
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Very pure halides Me2SbX (X - Br, I) are obtained by cleavage reactions of Me2SbSbMe2 with equimolar amount of Br2 or I2.Me3Sb and Me2SbI are formed in the reaction of Me2SbSbMe2 and MeI and a 1/1 molar ratio.With excess MeI the products are: Me4SbI2 and an adduct of composition MeSbI2 * 2Me4SbI, which can also be formed by the reaction of its components.
- Breunig, Hans Joachim,Jawad, Hussain
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p. 417 - 422
(2007/10/02)
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- Preparation and 121Sb M?ssbauer spectroscopy of methylchlorostibines
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The synthesis and 121Sb M?ssbauer spectra are reported for CH3SbCl2 and (CH3)2SbCl. The M?ssbauer spectroscopic data for the series (CH3)xSbCl3-x with x = 0-3 are discussed. The quadrupole coupling parameters of all four compounds can be explained qualitatively with a simple point charge model, assuming the bond angles between the ligands to be close to 90°. The isomer shift data indicate a decrease of s-electron density at the Sb nucleus with increase of x, which is ascribed to an increase of p character of the lone-pair electrons.
- Stevens,Trooster,Meinema,Noltes
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p. 801 - 803
(2008/10/08)
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- DARSTELLUNG UND SPECTROSKOPISCHE UNTERSUCHUNGEN VON METHYL- UND ISOPROPYLANTIMONHALOGENIDEN
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Halogenations of iPr3Sb yield the dihalides iPr3SbX2 X=Cl, Br, I.These compounds decompose thermally to iPrX and iPr2SbX.Halogenations of iPr2SbX produce unstable trihalides iPr2SbX3, which eliminate iPrX to give iPrSbX2.By this procedure only the bromides and iodides iPr2SbX and iPrSbX2 X=Br, I can be obtained in useful yields and purities.Pure iPrSbCl2 and iPr3Sb are products of exchange reaction of iPr2SbCl.The purity of the known methylcompounds Me2SbX X=Cl, Br, I obtained by decomposition of Me3SbX2 has been examined.MeSbI2 and Me3Sb are formed from Me2SbI.Previously unpublished ir-, 1H-nmr-, and ms-data of iPr3SbX2, R2SbX and RSbX2 R=Me, iPr, X=Cl, Br, I are discussed.
- Breunig, H. J.,Kanig, W.
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p. 149 - 160
(2007/10/02)
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- Gas-phase calorimetry of trimethyl group Va bases with boron Lewis acids
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The reaction between the group Va Lewis bases trimethylphosphine, trimethylarsine, and trimethylstibine and the boron Lewis acids boron trifluoride, boron trichloride, boron tribromide, diborane, and trimethylborane has been studied using gas-phase calori
- Mente, Donald C.,Mills, Jerry L.,Mitchell, Roy E.
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p. 123 - 126
(2007/11/06)
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- Aqueous electrochemistry of quaternary organoantimony ions
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The series of quaternary organoantimony ions, (CH3)m(C6H5)m-4Sb + (m = 1-4), has been studied in aqueous solution using dc polarography, cyclic voltammetry, and controlled potential electrolysis. Tetramethylantimony ion undergoes a single two-electron reduction to trimethylantimony and methane. The other three ions in the series are reduced in two one-electron steps. The first electron transfer involves the formation of an antimony(IV) species which rapidly reacts with the electrode metal to form an organomercury radical and a trivalent organoantimony compound. The organomercury radical disproportionates to form a diorganomercury compound. The second electron transfer gives trivalent organoantimony compounds and hydrocarbons. In two of the three possible cases both methyl and phenyl groups are lost by the antimony. The relative losses are different following the first and second electron transfer. Two factors govern the loss of the hydrocarbon group: the stability of the resulting hydrocarbon radical or carbanion and the stability of the resulting antimony compounds.
- Kok, Gregory L.,Morris, Michael D.
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p. 2146 - 2150
(2008/10/08)
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- The chloramination of some substituted stibines
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Trimethyl-, triethyl-, tri-n-propyl-, tri-n-butyl-, and triphenylstibines react with ammonia-free chloramine or an ammonia-chloramine mixture to produce compounds of the type [R3Sb(Cl)]2NH (I). These compounds readily hydrolyze to [R3Sb-(Cl)]2O (II ). Further reactions of II are also described. Infrared and proton magnetic resonance studies were carried out on compounds of types I and II and on a variety of other antimony compounds. Qualitative assignments of infrared bands are given.
- McKenney, Robert L.,Sisler, Harry H.
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p. 1178 - 1182
(2007/10/18)
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