cas 7550-35-8, Lithium bromide | Articles data

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Bridging and terminal coordination of Ga-Ga bonds by the chelating ligands imidotetraphenyldiphosphinate and -dithiodiphosphinate
Tetrakis[bis(trimethylsilyl)methyl]digallane(4) (1) reacted with imidotetraphenyldiphosphinic acid to yield two products, which were separated by recrystallization: The first one, bis[bis(trimethylsilyl)methyl]-imidotetraphenyldiphosphinato-O,O′-gallium (2), resulted from the cleavage of the Ga-Ga bond and contained a dialkylgallium unit, which was coordinated by a chelating imidodiphosphinato ligand. The digallium compound 1,2-bis[bis(trimethylsilyl)-methyl]-bis(μ-tetraphenyldiphosphinato-O, O′)digallium (3) was formed as the second product by a substituent exchange reaction and the release of bis(trimethylsilyl)methane. Its Ga-Ga bond (245.7 pm) was bridged by two imidodiphosphinato ligands. In contrast, the reaction of digallane(4) 1 with the sulfur derivative imidotetraphenyldithiodiphosphinic acid afforded a complicated mixture of unknown products. A compound analogous to 3 containing two imidodithiodiphosphinato ligands (5) was, however, obtained in a moderate yield by the precipitation of lithium acetate, when we treated dialkyldi(μ-acetato)digallium (4) with lithium imidotetraphenyldithiodiphosphinate. Remarkably, the chelating ligands did not adopt a bridging position across the Ga-Ga bond (249.9 pm) similar to 3, but each one was terminally coordinated to one Ga atom.
Uhl, Werner,Spies, Thomas,Saak, Wolfgang
p. 2095 - 2102
(1999)
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[GA16(PtBu2)10]: A gallium phosphide sheathed core of four naked Ga atoms?
Like inverse P4O10, a nearly tetrahedral Ga4P10 shell encloses a gallium-rich core with a distorted tetrahedral Ga4 center in the neutral metalloid cluster compound [Ga16(PtBu2)10].
Steiner, Jochen,Stoesser, Gregor,Schnoeckel, Hansgeorg
p. 1971 - 1974
(2003)
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Reactions of 1-hydro-and 1-halosilatranes with metal salts
1-Hydrosilatrane reduces AgNO3 and CuCl2 in CH 3CN to form metallic silver and CuCl, respectively; other reaction products are the silatranyl nitrate O2NOSi(OCH2CH 2)3N and the 1
Lazareva,Pestunovich
p. 751 - 752
(2006)
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Competitive interactions and glassy state extension in lithium salt solutions
We report measurements of high- and low-temperature limits of the liquid states of aqueous solutions for two common aqueous salt solutions. The liquid range extends from the glass transition temperature to the boiling point, and is maximized when the anion basicity is minimized. These limits and other characteristic temperatures have been determined by DTA and DSC studies of solution samples which are used to generate the most complete phase diagram yet available for the LiBr + H2O system. The glass-formation region has been extended by developing an emulsification technique suitable for use with concentrated aqueous salt solutions. Comparison of boiling points, liquidus temperatures, and glass transition temperatures shows that the reduction of the water content below 3H2O per Li+ is accompanied by important energetic effects. These are not present in the corresponding lithium acetate solutions, which exhibit relatively much lower boiling points. This is attributed to the stronger water - anion interaction in the lithium acetate system which is proportional to the anion basicity. Water activity increases and boiling points are lowered when the anions are more basic, but total cohesion, manifested by the glass transition temperature, increases. By contrast, addition of anion complexing salts such as ZnBr2 and ZnCl2 to LiBr-H2O solutions to reduce the anion basicity results in increased boiling points to over 200 ?°C as well as decreased crystallization temperatures. ? 1999 American Chemical Society.
Sivaraman, Alwarappa,Senapati, Hema,Angell, C. Austen
p. 4159 - 4163
(1999)
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OXIDATIVE EXTRACTION AND ION-EXCHANGE OF LITHIUM IN Li//2MoO//3: SYNTHESIS OF Li//2// minus //xMoO//3 (O less than multiplied by less than equivalent to 2. 0) AND H//2MoO//3** plus .
It is shown that lithium can be oxidatively extracted from Li//2 MoO//3 at room temperature using Br//2 in CHCl//3. The delithiated oxides, Li//2// minus //x MoO//3 (0 less than multiplied by less than equivalent to 1. 5) retain the parent ordered rocksalt structure. Complete removal of lithium from Li//2MoO//3 using Br//2 in CH//3CN results in a poorly crystalline MoO//3 that transforms to the stable structure at 280 degree C. Li//2MoO//3 undergoes topotactic ion-exchange in aqueous H//2SO//4 to yield a new protonated oxide, H//2MoO//3.
Gopalakrishnan, J.,Bhat, Vasudeva
p. 769 - 774
(1987)
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In44 mit In4-Tetraeder und In4Se44 mit In4Se4-Heterocubanstruktur
The reaction of InIBr with LiC(SiMe3)3*2THF yields the In(I) alkyl In44 1 in 70percent yield. 1 was characterized by a crystal structure determination showing a nearly undistorted In4 tetrahedron with mean In-In distances of 300.2(1) pm.Reaction of 1 with elemental Se gives In4Se44 2 with a slightly distorted In4Se4 hetero cubane structure.Keywords: Indium; Tetrahedron; X-ray structure; Cluster; Selenium; Heterocubane
Uhl, Werner,Graupner, Rene,Layh, Marcus,Schuetz, Uwe
p. C1 - C5
(1995)
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A Zinc Catalyzed C(sp3)?C(sp2) Suzuki–Miyaura Cross-Coupling Reaction Mediated by Aryl-Zincates
The Suzuki–Miyaura (SM) reaction is one of the most important methods for C?C bond formation in chemical synthesis. In this communication, we show for the first time that the low toxicity, inexpensive element zinc is able to catalyze SM reactions. The cross-coupling of benzyl bromides with aryl borates is catalyzed by ZnBr2, in a process that is free from added ligand, and is compatible with a range of functionalized benzyl bromides and arylboronic acid pinacol esters. Initial mechanistic investigations indicate that the selective in situ formation of triaryl zincates is crucial to promote selective cross-coupling reactivity, which is facilitated by employing an arylborate of optimal nucleophilicity.
Procter, Richard J.,Dunsford, Jay J.,Rushworth, Philip J.,Hulcoop, David G.,Layfield, Richard A.,Ingleson, Michael J.
supporting information
p. 15889 - 15893
(2017/10/24)

Synthesis, characterization, and catalytic behavior of methoxy- and dimethoxy-substituted pyridinium-type ionic liquids
Synthesis of methoxy-substituted pyridinium-type ionic liquids from a nontoxic and easy method is described. Catalytic behaviors of synthesized ionic liquids were investigated with various concentrations for the Mannich reaction. We have observed that methoxy- and dimethoxy-substituted pyridinium bromides showed better catalytic behavior than other ionic liquids.
Manikandan, Chitrarasu,Ganesan, Kilivelu
p. 3362 - 3367
(2014/12/11)

N-(2,4,6-trimethylborazinyl)-substituted phosphanes, arsanes, and stibanes
Reaction of the N-lithioborazine LiH2N3B 3Me3·OEt2 (2) in di ethyl ether with PCl3 or PBr3 leads to the borazinylphosphanes (Me 3B3N3H2)PX2, (Me 3B3N3H2)2PX (X = Cl, Br), and (Me3B3N3H2)3P, depending on the initial stoichiometry. The analogous arsane and stibane derivatives were obtained in a similar manner. While (Me3B 3N3H2)2PBr is reduced by LiAlH 4 in diethyl ether/hexane to give the monophosphane (Me 3B3N3H2)2PH (13), the reaction of (Me3B3N3H2)PBr 2 (5) with LiAlH4 in diethyl ether/hexane produces the zwitter-ionic compound [Me3B3N2(HN)] -P+H2Et (14). Dehalogenation of (Me 3B3N3H2)2PBr (6) with Na yields the diphosphane (Me3B3N3H 2)2PP(H2N3B3Me 3)2 (18), while the mixed diphosphane (Me 3B3N3H)2PPmes2 (17) is obtained from 6 and LiPmes2. Dehalogenation of Me3B 3N3H2PBr2 with Na results in the exclusive formation of (Me3B3N3H 2)4P4 (19), while the reaction of 5 with Li2Pmes leads to a mixture of cyclotetraphosphanes (mes) 4-n(Me3B3N3H2) nP4 (A-F) along with bicyclic P4mes 2. The new compounds have been characterized by NMR and IR spectroscopy and partly by mass spectrometry. X-ray structures for compounds, 4, 5, 6, 9, 13, 14, 17, 18, 19, and E have been determined. All show different B-N bond lengths within the borazine rings, and some have borazine rings in a half-chair conformation. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
Noeth, Heinrich,Gemuend, Birgit,Paine, Robert T.
p. 4282 - 4297
(2008/03/13)

PROCESS FOR THE RECOVERY OF MATERIALS FROM A DESULFURIZATION REACTION
Disclosed herein is an improved method for regenerating materials from a desulfurization/demetallation reaction. The desulfurization/demetallation reaction preferably has products including one or more of an alkali sulfide, polysulfide or hydrosulfide, or alkali earth sulfide, polysulfide, or hydrosulfide. The method includes the steps of reacting the desulfurization/demetallation products with a halogen, liberating and removing sulfur from the product, and then electrolyzing the halogenated products to separate the halogen from the alkali metal or alkali earth metal.
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(2010/02/13)

Technology for joint production of bromine and lithium bromide from brines from Siberian platform
Two methods for obtaining bromine and lithium bromide from highly mineralized brines enriched with lithium- and bromine-containing compounds, with Li:Br atomic ratio of 0.4-0.8, were studied. These methods are based on a combination of the technique for production of bromine and sorption recovery of lithium from brines to give eluates, LiCl solutions.
Ryabtsev,Kotsupalo,Serikova,Menzheres,Mamylova
p. 1891 - 1895
(2007/10/03)

Synthesis and structures of magnesium alanate and two solvent adducts
A synthesis and purification method for Mg(AlH4)2 is presented, which is based on a metathesis reaction of NaAlH4 and MgCl2 in diethyl ether and subsequent purification procedure leading to a high yield of the monoether adduct of Mg(AlH4)2. After removal of the solvent, the alanate has been obtained as a nanocrystalline material with a yield of 81% and a purity of 95%. Crystal structures were determined and discussed for the solvent adducts Mg(AlH4)2·4THF and Mg(AlH4)2·Et2O. A proposition is made for the structure of Mg(AlH4)2. Elsevier Science B.V. All rights reserved.
Fichtner, Maximilian,Fuhr, Olaf
p. 286 - 296
(2008/10/08)

Highly electrophilic olefin polymerization catalysts. Quantitative reaction coordinates for fluoroarylborane/alumoxane methide abstraction and ion-pair reorganization in group 4 metallocene and 'constrained geometry' catalysts
Reaction enthalpies of group 4 metallocenes having the general formula L2M(CH3)2 (L = Cp, 1,2-Me2Cp, Me5Cp; L2 = Me2Si(Me4Cp)((t)BuN); M = Ti, Zr, and Hf) with the strong organo-Lewis acid B(C6F5)3 were measured using batch titration calorimetry in toluene. Methide abstraction to form the corresponding L2MCH3+CH3B(C6F5)3- contact ion pairs is highly exothermic in all cases. Exothermicity increases with increasing Cp methyl substitution: for M = Zr, ΔH = -23.1(3), -24.3(4), and -36.7(5) kcal mol-1 for L = Cp, Me2Cp, and Me5Cp, respectively for M = Hf and L = 1,2-Me2Cp, ΔH = -20.8(5) kcal mol-1. 'Constrained geometry' complexes (L2 = Me2Si(Me4Cp)((t)BuN)) exhibit similar exothermicities, with ΔH = -22.6(2), -23.9(4), and -19.3(6) kcal mol-1 for M = Ti, Zr, and Hf, respectively. In contrast, analogous reactions with methylalumoxane (M:Al = 1:50) are less exothermic, with ΔH = -10.9(3) and -8.9(4) kcal mol-1 for L = 1,2-Me2Cp and M = Zr and Hf, respectively. Under identical conditions, (1,2-Me2Cp)2M-(CH3)2 (M = Zr, Hf) complexes also undergo methide abstraction with the less Lewis-acidic triarylboranes (C6F5)2BAr (AT = 3,5-C6H3F2, Ph, and 3,5-C6H3Me2); however, conversions to the corresponding (Me2-Cp)2MCH3+ CH3B(C6F5)2Ar- ion pairs, are incomplete. Variable-temperature NMR measurements yield thermodynamic parameters for partial methide abstraction by these less Lewis-acidic boranes. For Ar = 3,5-C6H3F2, ΔH = -18.7(7) and -15.2(8) kcal mol-1 with ΔS = -42(2) and -35(3) e.u:; for Ar = Ph, ΔH = -14.8(8) and -13.3(6) kcal mol-1 with ΔS = -31(2) and -39(2) e.u.; for Ar = 3,5-C6H3Me2, ΔH = -10.8(6) and -12.7(5) with ΔS = -19(2) and -36(4) e.u., in each case for M = Zr and Hf, respectively. Dynamic NMR analyses reveal that the activation barriers for methide abstraction from the neutral metallocene dialkyls are small and relatively insensitive to the borane identity (AH = 2-6 kcal mol-1) while ion-pair separation/recombination processes are greatly facilitated by polar solvents. Ethylene polymerization activities for eight (Me2Cp)2MCH3+CH3B(C6F5)2Ar- complexes measured in toluene solution (25°C, 1 atm) follow a trend in metal (Zr > Hf)as well as a substantial trend in triarylborane (Ar = C6F5 > 3,5-C6H3F2 > Ph ~3,5-C6H3-Me2). Polymerization activities correlate roughly with MCH3+ 13C NMR chemical shifts and enthalpies of methide abstraction.
Deck, Paul A.,Beswick, Colin L.,Marks, Tobin J.
p. 1772 - 1784
(2007/10/03)

Heterogeneous solution reactions between MBr3 (M = Ga, In) and Li3N. Formation and characterization of nanocrystalline GaN powders
Heterogeneous reactions between MBr3 (M = Ga, In) and LI3N in refluxing aromatic or aromatic/diglyme solvents were investigated as a potential route to nanocrystalline GaN and InN powders. For M = Ga, the pyrolysis of the as-prepared precursors at 450-500°C under vacuum or NH3 yielded nanosized GaN and elemental Ga. Gallium nitride was characterized by XRD, XPS and UV/vis spectroscopies, TEM microscopy, and elemental analysis. For M = In, the reactions were highly solvent dependent and resulted exclusively in redox products such as indium(I) bromide, InBr, and elemental In. Gauthier-Villars.
Wells,Janik
p. 1079 - 1090
(2008/10/08)

Contribution to the Chemistry of Boron, 222. Chemistry of Diborane(4) Derivatives: Mixed Tetraaminodiboranes(4) and Additions of Diborane(4) Derivatives to an Amino-imino-borane
Several transamination reactions of B2(NMe2)4 (1a) with secondary amines have led to mixed tetraaminodiborane(4) compounds B2(NMe2)4-n(NR2)n (2-4), and B2(NC5H10)4 (1d) has been characterized by an X-ray structure analysis which reveals the presence of a rather long B-B bond (1.75 Angstroem).However, tetraaminodiboranes(4) of type R2N(Me2N)B-B(NMe2)NR2 are more readily accessible from LiNR2 and B2(NMe2)2Cl2.Similarly, amination of B2(NMe2)2Cl2 with N,N'-dimethylethylenediamine (7) yields B--N,N'-dimethyl-1,3,2-diazaborolidine (8), while reactions with Li(Me)N-CH2-CH2-N(Me)Li (9) lead also to 2,3-bis(dimethylamino)-1,4-dimethyl-1,4,2,3-diazadiborinane (10) as the kinetically controlled product.This is further substantiated by the reaction of the B2(NMe2)2Br2 with 9 which gives exclusively the corresponding 1,4,2,3-diazadiborinane 11.Diborane(4) dihalides B2(NMe2)2X2 (X = Cl, Br) react only in 1:1 ratio with tmp-BN-CMe3 (13) leading to 14a, b.However, both a 1:1 and 1:2 methoxyboration of 13 has been observed with B2(OMe)4 with formation of 15 and 16. - Key Words: Diborane(4), tetraamino-, derivatives / Diborane(4), tetrapiperidino / 1,2,3,6-Diazadiborinane derivatives / Haloboration / Methoxyboration
Loderer, Dirk,Noeth, Heinrich,Pommerening, Hans,Rattay, Wilfried,Schick, Hannes
p. 1605 - 1612
(2007/10/02)

Contribution to the Chemistry of Boron, 224 Reactions and Structure of Electron-Precise Triborane(5) and Tetraborane(6) Derivatives
An improved synthesis of B3(NMe2)5 (2), B4(NMe2)6 (1), and B6(NMe2)8 (4) is reported.From each compound two of the four terminal dimethylamino groups are readily replaced by halogen atoms yielding α,ω-dihalides Bn(NMe2)nX2 (n = 3, 4; X = Cl, Br, I).These are used in turn to replace the substituent X by groups like RO, RS, RHN, R2P, and R.Crystal structure determinations on several of these compounds reveal as a common feature planar (C2N)BB2 and (C2N)B(B)X groups which are arranged in an approximately orthogonal manner to one another with NBBN dihedral angles ranging from 69 to 104.6 deg.Consequently, there is no significant ? bonding between the boron atoms. - Key Words: Triboranes(5), 1,ω-disubstituted / Tetraboranes(6), 1,ω-disubstituted / Hexaborane(8), octakis(dimethylamino)- / Electron-precise polyboranes
Linti, Gerald,Loderer, Dirk,Noeth, Heinrich,Polborn, Kurt,Rattay, Wilfried
p. 1909 - 1922
(2007/10/02)

On the Chemistry of Gallium Compounds, IV. - Synthesis and Structure of Monomeric (2,2,6,6-Tetramethylpiperidino)gallanes
Monomeric dimethyl- and diethyl(2,2,6,6-tetramethylpiperidino)gallanes have been synthesized and spectroscopically characterized.Starting from bis(2,2,6,6-tetramethylpiperidino)gallium halides (tmp)2GaX (16, 17, X = Cl, Br) various (aryloxy)- and organylbis(amido)gallium compounds (tmp)2GaY (18-21, Y = OAr, Ph, Me) have been obtained.The crystal structures of (tmp)2GaOPh (18) and (tmp)2GaPh (20) show trigonal planar-coordinated gallium atoms.Planar-coordinated nitrogen atoms with a GaN bond length of 188 pm are present in 20.In contrast, 18 shows one planar- and one slightly pyramidal-coordinated nitrogen atom, and this results in two different bond lengths of 184.9 and 181.8 pm, respectively. - Key Words: Gallium monoamides / Bisamidogallium halides / Organylgallium bisamides / Aryloxygallium bisamides
Linti, Gerald,Frey, Ronald,Polborn, Kurt
p. 1387 - 1394
(2007/10/02)

Synthesis, properties, and structural investigations of 1,3,2-diazaborolidines and 2,3-dihydro-1H-1,3,2-diazaboroles
A series of variously substituted 1,3,2-diazaborolidines have been prepared by different methods. 1,3-Diisopropyl-2-methyl-1,3,2-diazaborolidine (1a), 1,3-diethyl-2-methyl-1,3,2-diazaborolidine (2a), 1-ethyl-2,3-dimethyl-1,3,2-diazaborolidine (3a), and 1,2,3-trimethyl-1,3,2-diazaborolidine (4a) are formed from the corresponding lithiated ethylenediamines and CH3BBr2 in diethyl ether (method C). 2-Methyl-1-(trimethylsilyl)-1,3,2-diazaborolidine (5a), 1-tert-butyl-2-methyl-1,3,2-diazaborolidine (6a), and 1-isopropyl-2-methyl-1,3,2-diazaborolidine (7a) can be prepared either by method C, by method A, using the ethylenediamines and H3CB[N(CH3)2]2 to eliminate HN(CH3)2, or by method B, starting with CH3BBr2, NR3, and the corresponding ethylenediamines. The unsaturated 2,3-dihydro-1H-1,3,2-diazaboroles 1b-7b are synthesized by catalytic dehydrogenation in either liquid (1b-3b) or gaseous (4b-7b) state. Diazaboroles can act as 6-π-electron donors in Cr(CO)3 complexes. 1b-4b react with (CH3CN)3Cr(CO)3 under various conditions to form the corresponding complexes 1c-4c. The monosubstituted rings 5b-7b are not suited to form stable Cr(CO)3 complexes. One of the two rings in 8 can be combined with a Cr(CO)3 fragment to give 9. The yellow 1H-1,3,2-diazaborole-tricarbonylchromium complexes 1c-4c decompose slowly at room temperature. 2,3-Dihydro-2-methyl-1,3-bis(trimethylsilyl)-1H-1,3,2-diazaborole (10) can be metalated at one N atom by NaNH2 and K(O-t-Bu) to give the salts 11a and 11b. These alkali-metal derivatives can easily be protonated by HCl or CH3OH to form the N-H derivative 5b. X-ray structure analyses have been performed on the diazaborolidines 2a and 4a and on the diazaboroles 1b, 2b, 4b, and 8. The structures of 2a and 4b have been determined at two different temperatures. 1b, 2b, and 2a crystallize in the monoclinic space groups P21/n, P21/c, and Cc, respectively. 4a crystallizes hexagonally in the space group P32; 4b, tetragonally in the space group P42. X-X-Difference electron densities of 4a, 2a, and 4b show that the B-N bonds in the saturated compounds 4a and 2a possess remarkable double-bond character. The electron distribution in the 1,3,2-diazaborole 4b corresponds with that in 6-π-electron systems.
Schmid, Günter,Polk, Michael,Boese, Roland
p. 4421 - 4429
(2008/10/08)

Benzyltitanium and -zirconium cobalt carbonyls. Preparation and spectroscopic characterization
Tetrabenzyltitanium (1a) and -zirconium (1b) react with equimolar HCo(CO)4 (2) to give the corresponding tribenzylmetal-cobalt tetracarbonyl (M = Ti, 5a; M = Zr, 5b) derivatives. Compounds 5 also can be obtained from (PhCH2)3/s
Bartik, Tamás,Happ, Berit,Sorkau, Angela,Thiele, Karl-Heinz,Pályi, Gyula
p. 558 - 560
(2008/10/08)

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3-Bromo-1,2,3-dithiaboroles react with Grignard reagents by formation of 3-al-kyl(aryl)-1,2,3-dithiaboroles, which, upon reaction with isocyanates leads to the 2,3-dihydro-4H-1,3,2-thiazaborine-4-ones. 1H, 11B, 13C NMR and
Habben, Carl D.
p. 289 - 297
(2007/10/02)

Tetrakisdiindan(4) mit Indium-Indium-Bindung
The reaction of In2Br4*2TMEDA with lithium-bis(trimethylsilyl)methyl forms tetrakisindane(4) (1), having an indium-indium bond and precipitating from n-pentane as orange-red crystals.Though the molecular structure of 1 closely r
Uhl, Werner,Layh, Marcus,Hiller, Wolfgang
p. 139 - 154
(2007/10/02)

Aminoiminoboranes as Synthons for the Preparation of Three- and Four-Membered Rings with the Ring-Atom Sequence BNE, BNBE, BNSiE, and NBNE (E = P, Partly also B, Si, Ge, As)
Dihalides AHal2 add to the iminoborane iPr2NBNtBu (1a) to give diaminoboranes iPr2NB(Hal)N(tBu)-AHal (2a-i) and the triaminoborane (iPr2N)2BN(tBu)-AsBr2 (2j); by the substitution of Hal by NiPr2 or Me in 2e, f, j the derivatives 2k-m are formed.With the aid of alkali metal, the diaminoboranes 2a, c, d, m are dehalogenated to the three-membered ring compounds N(tBu)-A-> with A = B(NiPr2) (3), SiR2 (4a, b), P(NiPr)2 (5), whereas the dechlorination of 2a, c with Li2EPh (E = P, As) yields the four-membered ring products N(tBu)-A-E(Ph)-> with A = B(NiPr2) (6, 7), SiMe2 (8, 9).Dichlorides ACl2 are added to the iminoborane Me3Si(tBu)NBNtBu (1b) to give either the diaminoboranes Me3Si(tBu)NB(Cl)N(tBu)-ACl (2n-w) or the four-membered rings B(Cl)N(tBu)-A-> with A = GeMe2 (12), PX (13a-e), AsCl (14a), Me3SiCl being a second product.The same type of ring compound with A = BX (10a-d), SiX2 (11a, b) is formed from 2n-s during the elimination of Me3SiCl by the action of the solvent chloroform at room temperature.The Cl atom in these ring compounds can be substituted by alkyl, amino, or alkoxy groups to give 10e, f, 13f-h, 14b-j.The configuration and conformation of the products in solution and the structure of 3, 6, 7, 12, 14b in the solid state are discussed on the basis of NMR and X-ray data, respectively.
Bonn, Karl-Heinz van,Schreyer, Peter,Paetzold, Peter,Boese, Roland
p. 1045 - 1058
(2007/10/02)

Contributions to the Chemistry of Phosphorus, 182. - Li2P26R2 and LiP26R3 (R = Me, Et) - the First Partially Metalated Hexacosaphosphanes(4)
The triorganylhexacosaphosphides LiP26Me3 (2a) and LiP26Et3 (2b) have been obtained as the final products in the reaction of tetralithium hexacosaphosphide, Li4P26*16 THF, with methyl and ethyl bromide, respectively.The diorganylhexacosaphosphides Li2P26Me2 (1a) and Li2P26Et2 (1b) are formed as intermediates.According to NMR spectroscopic investigations the organyl substituents are arranged in the deltacyclane-analogous P9(3) end groups and in the case of 2 additionally in one of the two norbornane-analogous P7(5) middle groups of the P26(4) skeleton.A substitution at the P(-) atom of the second P7(5) group with formation of the fully alkylated hexacosaphosphanes(4), P26R4, does not occur due to steric reasons.
Baudler, Marianne,Becher, Rainer,Germeshausen, Joachim
p. 173 - 176
(2007/10/02)

Synthesis and characterization of neopentylaluminum compounds
The series of neopentylaluminum compounds, Al(CH2CMe3)3, Al(CH2CMe3)2H, Al(CH2CMe3)2Br, (Me3CCH2)2AlPPh2, and (Me3CCH2)2AlN(Me)H, have been prepared by reactions typical in organoaluminum chemistry and characterized by elemental and/or group analysis, cryoscopic molecular weight measurements in benzene solution, and IR and NMR spectroscopic data. All compounds in this series, except Al(CH2CMe3)3, are associated in benzene solution. Even though the neopentyl group is considered a bulky ligand with significant eteric effects, the Lewis acidity of Al(CH2CMe3)3 has been established by the formation and characterization of adducts LiAl(CH2CMe3)4, (Me3CCH2)3Al·PPh2H, and (Me3CCH2)3Al·N(Me)H2. However, since Al(CH2CMe3)3 is monomeric in benzene solution, the factors influencing the degree of association of organoaluminum compounds are discussed. The crystalline hydride Al(CH2CMe3)2H has been prepared from Al(CH2CMe3)3 and LiAlH4. The other product was LiH rather than LiAl(CH2CMe3)H3. These observations of products are unusual in organoaluminum chemistry.
Beachley Jr.,Victoriano
p. 63 - 67
(2008/10/08)

REACTIONS OF SULFINYL CARBANIONS WITH ORGANOMETALLIC COMPOUNDS: PREPARATION OF
Sulfinyl carbanions, -Li+ (R = Ph, Me; R' = H, Ph) have been observed to have often low reactivity towards neutral transition metal organometallic systems.When reactions do occur they usually involve salt eliminations and
Lucas, C.R.
p. 281 - 292
(2007/10/02)