共查询到20条相似文献,搜索用时 31 毫秒
1.
Ryan M. Tipker Jake A. Muldoon Daniel H. Pham Balazs R. Varga Russell P. Hughes David S. Glueck Gary J. Balaich Arnold L. Rheingold 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2022,134(1):e202110753
Tetrahedral main-group compounds are normally configurationally stable, but P-epimerization of the chiral phosphiranium cations syn- or anti-[Mes*P(Me)CH2CHPh][OTf] (Mes*=2,4,6-(t-Bu)3C6H2) occurred under mild conditions at 60 °C in CD2Cl2, resulting in isomerization to give a syn-enriched equilibrium mixture. Ion exchange with excess [NBu4][Δ-TRISPHAT] (Δ-TRISPHAT=Δ-P(o-C6Cl4O2)3) followed by chromatography on silica removed [NBu4][OTf] and gave mixtures of syn- and anti-[Mes*P(Me)CH2CHPh][Δ-TRISPHAT]?x[NBu4][Δ-TRISPHAT]. NMR spectroscopy showed that isomerization proceeded with epimerization at P and retention at C. DFT calculations are consistent with a mechanism involving P-C cleavage to yield a hyperconjugation-stabilized carbocation, pyramidal inversion promoted by σ-interaction of the P lone pair with the neighboring β-carbocation, and ring closure with inversion of configuration at P. 相似文献
2.
Dialkylaminostibanes. Preparation and Spectra The dialkylaminodichlorostibanes Cl2SbNMe2 ( 1 ), Cl2SbNMeEt ( 2 ), and Cl2SbNEt2 ( 3 ) as well as the bis(dialkylamino) chlorostibanes ClSb[NMe2]2 ( 4 ), ClSb[NMeEt]2 ( 5 ), and ClSb[NEt2]2 ( 6 ) were prepared by exchange reactions between SbCl3 and Sb[NRR′]3 (R = R′ = Me ( 7 ); R = R′ = Et ( 8 ); R = Me, R′ = Et ( 9 ). By reaction of 1 and 2 with MeOH and EtOH the dialkylaminoalkoxochlorostibanes ClSbOMe[NMe2] ( 10 ), ClSbOEt[NMe2] ( 11 ), and ClSbOEt[NMeEt] ( 12 ) can be prepared. The vibrational spectra of 1–12 were assigned and discussed. 1–4 and 10–12 were associated in the solid state by SbN-bridges to dimeres. An analog association is sterically hinderd for 5–9 . 相似文献
3.
Polychloride monoanions [Cln]‐ (n = 3, 5, 7, 9) stabilized by quaternary ammonium salts are obtained through the addition or condensation of an excess of dry chlorine to [NMe4]Cl, [NEt4]Cl, [NPr4]Cl, or [NBu4]Cl and characterized by Raman spectroscopy and state‐of‐the‐art quantum chemical calculations up to the CCSD(T) level. 相似文献
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Thiochloro Anions of Molybdenum (IV). Crystal Structure of (NEt4)3[Mo3(μ3-S)(μ-S2)3Cl6]Cl μ CH2Cl2. Crystal Structure, Magnetic Properties, and EPR-Spectrum of (NEt4)2 [Mo2(μ-S2)(μ-Cl)2Cl6] From molybdenum pentachloride and tetraethylammonium hydrogensulfide in CH2Cl2 an insoluble product of composition (NEt4)2[Mo2S3Cl9] was obtained along with a brown solution, from which (NEt4)2[Mo2(S2)Cl8] was crystallized. The insoluble product and NEt4Cl react in CH2Cl2 to yield, among others, (NEt4)3[Mo3(S)(S2)3Cl6]Cl · CH2Cl2. The latter crystallizes in the orthorhombic space group Pnma, a = 2495.8, b = 1501.2, c = 1295.6 pm, Z = 4. According to the crystal structure determination (3070 observed reflexions, R = 0.049) the [Mo3(S)(S2)3Cl6]2? ion consists of an Mo3 triangle with Mo? Mo bonds, each side of the triangle is bridged by disulfido groups and one sulfur atom is capped over the Mo3 triangle; the single chloride ion is looseley associated to three S atoms. (NEt4)2[Mo2(S2)Cl8] also crystallizes in the space group Pnma, a = 1425.6, b = 1129.9, c = 2004.7 pm, Z = 4; structure determination with 1703 observed reflexions, R = 0.061. In the [Mo2(S2)Cl8]2? ion the Mo atoms are bridged via one disulfido group and two chlorine atoms. There is a Mo? Mo bond, but according to the magnetic properties and the EPR spectrum each Mo atom still possesses one unpaired electron. 相似文献
6.
M. I. Shilina V. B. Barabash V. V. Smirnov Yu. A. Serguchev 《Theoretical and Experimental Chemistry》1993,28(2):136-139
The kinetics and mechanism of the chlorination of C3H5Cl were studied in a broad interval of temperatures and reactant concentrations. Competition was found between homolytic and nonradical chlorination of C3H5Cl in liquid phase in a nonpolar solvent. It was shown that for [C3H5Cl] < 0.1 M and T < 270 K the main reaction is the nonradical reaction, which has a negative temperature coefficient. The kinetics of the nonradical chlorination of C3H5Cl is dependent on the concentration of chlorine and is described by the sum of kinetic reactions of overall second and third orders. If [Cl2] > 1.5 M the main reaction is the reaction involving two molecules of chlorine and one molecule of olefin.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 28, No. 2, pp. 155–158, March–April, 1992. 相似文献
7.
Osvaldo Ordoñez Dr. Xiaojuan Yu Dr. Guang Wu Dr. Jochen Autschbach Dr. Trevor W. Hayton 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(19):5885-5889
Reaction of [UO2Cl2(THF)3] with 3 equivalents of LiC6Cl5 in Et2O resulted in the formation of first uranyl aryl complex [Li(Et2O)2(THF)][UO2(C6Cl5)3] ([Li][ 1 ]) in good yields. Subsequent dissolution of [Li][ 1 ] in THF resulted in conversion into [Li(THF)4][UO2(C6Cl5)3(THF)] ([Li][ 2 ]), also in good yields. DFT calculations reveal that the U−C bonds in [Li][ 1 ] and [Li][ 2 ] exhibit appreciable covalency. Additionally, the 13C NMR chemical shifts for their Cipso environments are strongly affected by spin-orbit coupling—a consequence of 5f orbital participation in the U−C bonds. 相似文献
8.
Hechun Lin Peter W. de Oliveira Ingrid Grobelsek Aude Haettich Prof. Dr. Dr. h. c. Michael Veith 《无机化学与普通化学杂志》2010,636(11):1947-1954
The solvothermal reactions of Ti(OiPr)4 in alcohol using ionic liquid as additive were investigated. In the presence of [BMIM][Cl], [BMIM][Br], [BMIM][NTf2], [BMIM][SO3Me], [BMIM][SO4Me], or [BMIM][OTf] (BMIM = 1‐Butyl‐3‐methylimidazolium), pure anatase nanoparticles were obtained. The controlled hydrolysis of Ti(OiPr)4 in the presence of ionic liquids to form titanium oxo clusters plays a key role in the formation of anatase nanostructures, and ionic liquids can be repeatedly used to synthesise anatase nanoparticles. However, in the presence of [BMIM][PF6], [BMIM]2[Ti(OH)6] was obtained by an anion exchange reaction. 相似文献
9.
Preparation and Vibrational Spectra of Dichloro and Dibromodithiophosphate. Crystal Structures of [PPh3Me][PS2Cl2] and [PPh4][PS2Br2] Dichloro and dibromodithiophosphates [Cat+][PS2X2?] with a large organic cation can be obtained from P4S10, CatX and HX in CH2Cl2 (Cat+ = PPh4+, PPh3Me+; X = Cl, Br). The vibrational spectra (i.r. and Raman) of the [PS2X2]? ions are reported and discussed; force constants were calculated. The crystal structures of [PPh3Me][PS2Cl2] and [PPh4][PS2Br2] were determined and refined with X-ray diffraction data. In both cases, simple anions [PS2X2]? are present. [PPh3Me][PS2Cl2]: orthorhombic, space group P212121, a = 1089, b = 1334, c = 1476 pm, Z = 4, refinement to a residual index R = 0.046 for 1116 reflexions; the structure is isotopic with [PPh3Me][VO2Cl2]. [PPh4][PS2Br2]: tetragonal space group I4 , a = 1301, c = 721 pm, Z = 2, refinement to R = 0.065 for 357 reflexions; the structure is isotypic with [AsPh4][FeCl4] with [PS2Br2]? ions occupying positions of 4 -symmetry with statistical orientation (statistical superposition of Br and S positions). 相似文献
10.
P. Prhm J. R. Schmid K. Sonnenberg P. Voßnacker S. Steinhauer C. J. Schattenberg R. Müller M. Kaupp S. Riedel 《Angewandte Chemie (International ed. in English)》2020,59(37):16002-16006
A facile one‐pot gram‐scale synthesis of tetraalkylammonium tetrafluoridochlorate(III) [cat][ClF4] ([cat]=[NEt3Me]+, [NEt4]+) is described. An acetonitrile solution of the corresponding alkylammonium chloride salt is fluorinated with diluted fluorine at low temperatures. The reaction proceeds via the [ClF2]? anion which is structurally characterized for the first time. The potential application of [ClF4]? salts as fluorinating agents is evaluated by the reaction with diphenyl disulfide, Ph2S2, to pentafluorosulfanyl benzene, PhSF5. The CN moieties in acetonitrile and [B(CN)4]? are transferred in CF3 groups. Exposure of carbon monoxide, CO, leads to the formation of carbonyl fluoride, COF2, and elemental gold is dissolved under the formation of tetrafluoridoaurate [AuF4]?. 相似文献
11.
Structural Chemistry of the Alkyl- and Arylhaloarsenates(III) [Me2As2Cl5]–, [RAsCl3]–, [R2As2Br6]2– (R = Me, Et, Ph) and [Ph2AsX2]– (X = Cl, Br) The alkyl- and arylhaloarsenates(III) [Ph4P][Me2As2Cl5] ( 1 ), [Ph4P][RAsCl3] (R = Me, Et, Ph, 2 – 4 ), [Me3PhN][PhAsCl3] ( 5 ), [Ph4P]2[R2As2Br6] (R = Me, Et, Ph, 6 – 8 ), [n-Pr4N][Ph2AsCl2] ( 9 ) and [n-Bu4N][Ph2AsBr2] ( 10 ) have been prepared and their structures established by X-ray diffraction. In contrast to the chloroarsenates(III) 2 – 5 , which all contain isolated ψ-trigonal bipyramidal anions [RAsCl3]–, the analogous bromoarsenates(III) 6 – 8 exhibit dimeric structures. Whereas the trans sited As–Cl distances in 2 and 3 are very similar a pronounced degree of asymmetry is apparent for the Cl–As–Cl three-centre bonds in 4 and 5 [2.396(1) and 2.602(1) Å in 5]. In 6 and 7 Ci symmetry related RAsBr2 units are connected through long As…Br bonds [2.926(1) and 3.116(2) Å in 6 ]. The bromophenylarsenate(III) anion of 8 which contains two effectively undistorted ψ-trigonal bipyramids [PhAsBr3]– associated by weak As…Br interactions [3.117(2) Å]. In view of its very long bridging As…Cl distances the [Me2As2Cl5]– anion in 1 can, as 6 an 7 , be regarded as two MeAsCl2 molecules weakly linked through a chloride ion. 相似文献
12.
Marco Reichel Cornelia Unger Sviatlana Dubovnik Andreas Roidl Andreas Kornath Konstantin Karaghiosoff 《Phosphorus, sulfur, and silicon and the related elements》2020,195(11):947-948
AbstractTertiary alkyl, aryl or amino phosphines PR3 (R?=?Me, nBu, C2H4CN, NEt2) and the bis(phosphine) POP were allowed to react with fluoroiodomethane to produce fluoromethyl phosphonium salts. New crystal structures of forming fluoromethyl phosphonium salts [R3PCH2F]I with R?=?Me, C2H2CN and NEt2 were obtained and gave additional information of the nearly unknown P-CH2F moiety. The toxicity of the water soluble salt [Me3PCH2F]I was investigated compared to the biocide THPS. 相似文献
13.
N‐Heterocyclic Olefin–Carbon Dioxide and –Sulfur Dioxide Adducts: Structures and Interesting Reactivity Patterns
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Dr. Lars H. Finger Jannick Guschlbauer Dr. Klaus Harms Prof. Dr. Jörg Sundermeyer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(45):16292-16303
Depending on the amount of methanol present in solution, CO2 adducts of N‐heterocyclic carbenes (NHCs) and N‐heterocyclic olefins (NHOs) have been found to be in fully reversible equilibrium with the corresponding methyl carbonate salts [EMIm][OCO2Me] and [EMMIm][OCO2Me]. The reactivity pattern of representative 1‐ethyl‐3‐methyl‐NHO–CO2 adduct 4 has been investigated and compared with the corresponding NHC–CO2 zwitterion: The protonation of 4 with HX led to the imidazolium salts [NHO–CO2H][X], which underwent decarboxylation to [EMMIm][X] in the presence of nucleophilic catalysts. NHO–CO2 zwitterion 4 can act as an efficient carboxylating agent towards CH acids such as acetonitrile. The [EMMIm] cyanoacetate and [EMMIm]2 cyanomalonate salts formed exemplify the first C?C bond‐forming carboxylation reactions with NHO‐activated CO2. The reaction of the free NHO with dimethyl carbonate selectively led to methoxycarbonylated NHO, which is a perfect precursor for the synthesis of functionalized ILs [NHO–CO2Me][X]. The first NHO‐SO2 adduct was synthesized and structurally characterized; it showed a similar reactivity pattern, which allowed the synthesis of imidazolium methyl sulfites upon reaction with methanol. 相似文献
14.
Alex S. Ionkin William J. Marshall Douglas J. Adelman Aaron L. Shoe Rupert E. Spence Tuyu Xie 《Journal of polymer science. Part A, Polymer chemistry》2006,44(8):2615-2635
A new series of nitro‐substituted bis(imino)pyridine ligands {2,6‐bis[1‐(2‐methyl‐4‐nitrophenylimino)ethyl]pyridine, 2,6‐bis[1‐(4‐nitrophenylimino)ethyl]pyridine, (1‐{6‐[1‐(4‐nitro‐phenylimino)‐ethyl]‐pyridin‐2‐yl}‐ethylidene)‐(2,4,6‐trimethyl‐phenyl)‐amine, and 2,6‐bis[1‐(2‐methyl‐3‐nitrophenylimino)ethyl]pyridine} and their corresponding Fe(II) complexes [{p‐NO2? o‐Me? Ph? N?C(Me)? Py? C(Me)?N? Ph? o‐ Me? p‐NO2}FeCl2 ( 10 ), L2FeCl2 ( 11 ), {m‐NO2? o‐Me? Ph? N?C(Me)? Py? C(Me)?N? Ph? o‐Me? m‐NO2}FeCl2 ( 12 ), and {p‐NO2? Ph? N?C(Me)? Py? C(Me)?N? Mes}FeCl2 ( 14 )] were synthesized. According to X‐ray analysis, there were shortenings of the axial Fe? N bond lengths (up to 0.014 Å) in para‐nitro‐substituted complex 10 and (up to 0.015 Å) in meta‐nitro‐substituted complex 12 versus the Fe(II) complex without nitro groups [{o‐Me? Ph? N?C(Me)? Py? C(Me)?N? Ph? o‐Me}FeCl2 ( 1 )]. Complexes 10 , 12 , and 14 afforded very active catalysts for the production of α‐olefins and were more temperature‐stable and had longer lifetimes than parent non‐nitro‐substituted Fe(II) complex 1 . The reaction between FeCl2 and a sterically less hindered ligand [p‐NO2? Ph? N?C(Me)? Py? C(Me)?N? Ph? p‐NO2] resulted in the formation of octahedral complex 11 . A para‐dialkylamino‐substituted bis(imino)pyridine ligand [p‐NEt2? o‐Me? Ph? N?C(Me)? Py? C(Me)?N? Ph? o‐Me? p‐NEt2] and the corresponding Fe(II) complex [{p‐NEt2? o‐Me? Ph? N?C(Me)? Py? C(Me)?N? Ph? o‐Me? p‐NEt2}FeCl2 ( 16 )] were synthesized to evaluate the effect of enhanced electron donation of the ligand on the catalytic performance. According to X‐ray analysis, there was a shortening (up to 0.043 Å) of the axial Fe? N bond lengths in para‐diethylamino‐substituted complex 16 in comparison with parent Fe(II) complex 1 . © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2615–2635, 2006 相似文献
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A. Müller A. Hildebrand E. Krickemeyer D. Slter H. Bgge A. Armatage 《无机化学与普通化学杂志》1992,614(8):115-120
(PPh4)[(ReO2S2)CuI] and (NEt4)2[ReOS3)Cu3Cl4]: Fixation of the up to now not Isolated Ions [ReO2S2]? and [ReOS3]? Utilizing the Stability of the CuS2(Re) and Cu3S3(Re) Fragments (PPh4)[(ReO2S2)CuI] ( 1 ) and (NEt4)2[ReOS3)Cu3Cl4] ( 2 ) containing the up to now not isolated oxothioperrhenate ions [ReO2S2]? and [ReOS3]? as ligands, have been prepared by the reaction of (NEt4)[ReS4] with PPh3 and CuI in acetone in the presence of (PPh4)I (( 1 )) or with CuCl in CH2Cl2 in the presence of (NEt4)Cl (( 2 )), respectively. 1 and 2 have been characterized by X-ray structure analysis, elemental analysis and spectroscopic studies (IR, UV/Vis). The electronic spectra show bands which can approximately be assigned to interesting low-energy charge-transfer-transitions of the type d(Cu) → d(Re). For crystal data see Inhaltsübersicht. 相似文献
17.
Uwe Dieckbreder Gerd‐Volker Rschenthaler Alexander A. Kolomeitsev 《Heteroatom Chemistry》2002,13(7):650-653
Bis(trifluoromethyl)phosphines RP(CF3)2 (R = Me, NEt2) were methylated by MeOSO2CF3, yielding the respective phosphonium salts [RP(CF3)2Me]+ and CF3SO3−. Deprotonation using MeNP(NEt2)3 led to the phosphorus ylides RP(CF3)2CH2, stable in solution at ambient temperature, which could be converted into 1,2λ5σ5‐oxaphosphetanes by adding hexafluoroacetone. © 2002 Wiley Periodicals, Inc. Heteroatom Chem 13:650–653, 2002; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10061 相似文献
18.
Reaction of [Ru(η6‐p‐cymene)Cl2]2 with two equivalents of [Ph4P][Cl] in CH2Cl2 yields [Ph4P][Ru(η6‐p‐cymene)Cl3], containing a trichlororuthenate(II) anion. In solution, an equilibrium between the product and [Ru(η6‐p‐cymene)Cl2]2 is observed, which in CDCl3 is nearly completely shifted to the dimer, whereas in CD2Cl2 essentially a 1:1‐mixture of the two ruthenium species is present. Crystallization from CH2Cl2/pentane yielded two different crystals, which were identified by X‐ray analysis as [Ph4P][Ru(η6‐p‐cymene)Cl3] and [Ph4P][Ru(η6‐p‐cymene)Cl3]·CH2Cl2. 相似文献
19.
Da‐Wei Fu Ji‐Xing Gao Wen‐Hui He Xue‐Qin Huang Yu‐Hua Liu Yong Ai 《Angewandte Chemie (International ed. in English)》2020,59(40):17477-17481
1,4‐Diazabicyclo[2.2.2]octane (dabco) and its derivatives have been extensively utilized as building units of excellent molecular ferroelectrics for decades. However, the homochiral dabco‐based ferroelectric remains a blank. Herein, by adding a methyl (Me) group accompanied by the introduction of homochirality to the [H2dabco]2+ in the non‐ferroelectric [H2dabco][TFSA]2 (TFSA=bis(trifluoromethylsulfonyl)ammonium), we successfully designed enantiomeric ferroelectrics [R and S‐2‐Me‐H2dabco][TFSA]2. The two enantiomers show two sequential phase transitions with transition temperature (Tc) as high as 405.8 K and 415.8 K, which is outstanding in both dabco‐based ferroelectrics and homochiral ferroelectrics. To our knowledge, [R and S‐2‐Me‐H2dabco][TFSA]2 are the first examples of dabco‐based homochiral ferroelectrics. This finding opens an avenue to construct dabco‐based homochiral ferroelectrics and will inspire the exploration of more eminent enantiomeric molecular ferroelectrics. 相似文献
20.
The first α‐diimine nickel(I) complex having a chloro bridge is reported. The centrosymmetric dinuclear structure of {[ArN?C(Me)C(Me)?NAr]NiCl}2[Ar?2,6?C6H3(i‐Pr)2] features two chelating α‐diimine ligands and two bridged chlorine atoms, so that a distorted tetrahedral N2Cl2 coordination geometry for nickel results. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献