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1.
Jacquelyn M. Burke Judith A. K. Howard Todd B. Marder Claire Wilson 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(11):1354-1355
The title compound, C21H22P+·BCl4?, is the first structurally characterized example of the [HP(o‐tolyl)3]+ cation, presented here with BCl4? as the counter‐ion. The cation has a near‐tetrahedral P atom and the BCl4? anion is near‐tetrahedral at boron. There are no unusually short cation–anion contacts. 相似文献
2.
Li6+2x[B10Se18]Sex (x ≈ 2), an Ion‐conducting Double Salt Li6+2x[B10Se18]Sex (x ≈ 2) was prepared in a solid state reaction from lithium selenide, amorphous boron and selenium in evacuated carbon coated silica tubes at a temperature of 800 °C. Subsequent cooling from 600 °C to 300 °C gave amber colored crystals with the following lattice parameters: space group I2/a (at 173 K); a = 17.411(1) Å, b = 21.900(1) Å, c = 17.820(1) Å, β = 101.6(1)°. The crystal structure contains a well‐defined polymeric selenoborate network of composition ([B10Se16Se4/2]6?)n consisting of a system of edge‐sharing [B10Se16Se4/2] adamantanoid macro‐tetrahedra forming large channels in which a strongly disorderd system of partial occupied Li+ cations and additional disordered Se2? anions is observed. The crystal structure of the novel selenoborate is isotypic to Li6+2x[B10S18]Sx (x ≈ 2) [1]. X‐ray and 7Li magic‐angle spinning NMR data suggest that the site occupancies of the three crystallographically distinct lithium ions exhibit a significant temperature dependence. The lithium ion mobility has been characterized by detailed temperature dependent NMR lineshape and spin‐lattice relaxation measurements. 相似文献
3.
Upon reacting SeCl4 with Me3Si–F–Al(ORF)3, the selenonium salt SeMeCl2[al‐f‐al] ( 1 ) {[al‐f‐al]– = [F[Al(OC(CF3)3)3]2]–} was obtained and characterized by NMR, IR, and Raman spectroscopy as well as single crystal XRD experiments. Despite the [SeX3]+ (X = F, Cl, Br, I) and [SeR3]+ salts (R = aliphatic organic residue) being well known and thoroughly studied, the mixed cations are scarce. The only previous example of a salt with the [SeMeCl2]+ cation is SeMeCl2[SbCl6], which was never structurally characterized and is unstable in solution over hours. Only 1H‐NMR studies and IR spectra of this compound are known. The unexpected use of Me3Si–F–Al(ORF)3 as a methylating agent was investigated via DFT calculations and NMR experiments of the reaction solution. The reaction of SeCl3[al‐f‐al] with Me3Si‐Cl at room temperature in CH2Cl2 proved to yield the same product with Me3Si–Cl acting as a methylating agent. 相似文献
4.
Syntheses and Crystal Structures of Copper and Silver Complexes with the Ylide Ph3PCHP(O)PPh2 as Ligand
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The reactivity of the hydrolysis product of hexaphenylcarbodiphosphorane, PPh3CHP(O)Ph2, towards different soft Lewis acids, such as CuI and Ag[BF4] are reported. While CuI exclusively binds at the ylidic carbon atom, reaction of the silver cation in CH2Cl2 leads to proton abstraction from the solvent to give the cation [PPh3CH2P(O)Ph2]+. Surprisingly, Ag+ replaces the methyl group of [PPh3CHMeP(O)Ph2]+ to produce a dimeric complex, in which Ag+ is coordinated to C and O forming an eight membered ring. The compounds were characterized by spectroscopic methods and X‐ray diffraction. 相似文献
5.
Novel Oxonium Halogenochalcogenates Stabilized by Crown Ethers: [H3O(Dibromo‐benzo‐18‐crown‐6)]2[Se3Br10] and [H5O2(Bis‐dibromo‐dibenzo‐24‐crown‐8]2[Se3Br8] Two novel complex oxonium bromoselenates(II,IV) and –(II) are reported containing [H3O]+ and [H5O2]+ cations coordinated by crown ether ligands. [H3O(dibromo‐benzo‐18‐crown‐6)]2[Se3Br10] ( 1 ) and [H5O2(bis‐dibromo‐dibenzo‐24‐crown‐8]2[Se3Br8] ( 2 ) were prepared as dark red crystals from dichloromethane or acetonitrile solutions of selenium tetrabromide, the corresponding unsubstituted crown ethers, and aqueous hydrogen bromide. The products were characterized by their crystal structures and by vibrational spectra. 1 is triclinic, space group (Nr. 2) with a = 8.609(2) Å, b = 13.391(3) Å, c = 13.928(3) Å, α = 64.60(2)°, β = 76.18(2)°, γ = 87.78(2)°, V = 1404.7(5) Å3, Z = 1. 2 is also triclinic, space group with a = 10.499(2) Å, b = 13.033(3) Å, c = 14.756(3) Å, α = 113.77(3)°, β = 98.17(3)°, γ = 93.55(3)°. V = 1813.2(7) Å3, Z = 1. In the reaction mixture complex redox reactions take place, resulting in (partial) reduction of selenium and bromination of the crown ether molecules. In 1 the centrosymmetric trinuclear [Se3Br10]2? consists of a central SeIVBr6 octahedron sharing trans edges with two square planar SeIIBr4 groups. The novel [Se3Br8]2? in 2 is composed of three planar trans‐edge sharing SeIIBr4 squares in a linear arrangement. The internal structure of the oxonium‐crown ether complexes is largely determined by the steric restrictions imposed by the aromatic rings in the crown ether molecules, as compared to complexes with more flexible unsubstituted crown ether ligands. 相似文献
6.
Hella Folkerts Kurt Dehnicke Jrg Magull Helmut Goesmann Dieter Fenske 《无机化学与普通化学杂志》1994,620(7):1301-1306
Phosphorane Iminato-Trichloroselenates(II): Syntheses and Crystal Structures of [SeCl(NPPh3)2]+SeCl3? and [Me3SiN(H)PMe3]2+[Se2Cl6]2? [SeCl(NPPh3)2]+SeCl3? has been synthesized by the reaction of Se2Cl2 with Me3SiNPPh3 in acetonitrile solution, forming orangered crystals, whereas red crystals of [Me3SiN(H)PMe3]2+[Se2Cl6]2? were obtained by the reaction of Me3SiNPMe3 with SeOCl2 in acetonitrile solution. Both complexes were characterized by X-ray structure determinations. [SeCl(NPPh3)2]+SeCl3?: Space group P21/n, Z = 4, structure solution with 7 489 observed unique reflections, R = 0.057. Lattice dimensions at ?60°C: a = 1 117.0; b = 2 241, c = 1 407.5 pm, β = 95.61°. In the cation [SeCl(NPPh3)2]+ the selenium atom is φ-tetrahedrally coordinated by the chlorine atom and by the nitrogen atoms of the phosphorane iminato ligands, whereas the anion SeCl3? has a T-shaped structure with φ-trigonal-bipyramidale surrounding of the selenium atom. [Me3SiN(H)PMe3]2+[Se2Cl6]2?: Space group P21/c, Z = 4, structure solution with 2 093 observed unique reflections, R = 0.080. Lattice dimensions at ?70°C: a = 956, b = 828, c = 1 973 pm, β = 93.80°. The structure consists of [Me3SiN(H)PMe3]+ ions and planar [Se2Cl6]2? anions, in which the selenium atoms are bridged nearly symmetrically by two chlorine atoms. 相似文献
7.
Xuean Chen Xiaoying Huang Jing Li 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(10):1181-1182
The title compound, tripotassium sodium tritin octaselenide, K3NaSn3Se8, has a molecular (zero‐dimensional) structure containing trimeric [Sn3Se8]4? units which consist of three edge‐sharing SnSe4 tetrahedra. The [Sn3Se8]4? anions and the tetrahedrally coordinated Na+ cations are arranged in an alternating fashion along the c axis to form SiS2‐like chains, which are then separated by eight‐coordinate K+ cations. The Sn—Se bond distances are normal, being in the range 2.477 (1)–2.612 (1) Å. 相似文献
8.
《无机化学与普通化学杂志》2018,644(10):483-488
Chlorosulfonamide reacts in the superacidic solutions HF/GeF4 and HF/AsF5 under the formation of ([ClSO2NH3]+)2[GeF6]2– and [ClSO2NH3]+[AsF6]–, respectively. The chlorosulfonammonium salts were characterized by X‐ray single crystal structure analysis as well as vibrational spectroscopy and discussed together with quantum chemical calculations. ([ClSO2NH3]+)2[GeF6]2– crystallizes in the triclinic space group P1 with one formula unit in the unit cell. [ClSO2NH3]+[AsF6]– crystallizes in the monoclinic space group P21/n with four formula units in the unit cell. Dependent on the counterion, [AsF6]– or [GeF6]2–, considerable structural differences of the [ClSO2NH3]+ cation are observed. Furthermore, the hitherto unknown X‐ray single crystal structure of chlorosulfonamide is determined in the course of this study. Chlorosulfonamide crystallizes in the orthorhombic space group Pmc2 with four formula units per unit cell. 相似文献
9.
New Class of Hydrido Iron(II) Compounds with cis‐Reactive Sites: Combination of Iron and Diphosphinodithio Ligand
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Jianguo Liu Fanjun Zhang Ailing Zhang Prof. Dr. Qingxiao Tong Prof. Dr. Chen‐Ho Tung Prof. Dr. Wenguang Wang 《化学:亚洲杂志》2016,11(16):2271-2277
The cationic complex [Fe(P2S2)(NCMe)2]2+ (P2S2=(Ph2PC6H4CH2S)2(C2H4) ([ 1 (NCMe)2]2+)), with two MeCN ligands in a cis orientation, was synthesized and characterized. The MeCN ligand in [ 1 (NCMe)2]2+ undergoes further substitution by a hydride ligand or CO to give iron(II) hydrides [H 1 (NCMe)]+, [H 1 H]0, and [H 1 (CO)]+. The order of reactivity of the hydrides was [H 1 H]0>[H 1 (NCMe)]+>[H 1 (CO)]+, and was illustrated by their reactions toward protic acids, the organic cation of 10‐methylacridinium (MeAcr+) as a hydride acceptor, and intermolecular hydride transfer reactions among these ferrous compounds. For example, MeAcr+ was reduced initially by a one‐electron transfer process from [H 1 H]0, resulting in competing reactions of MeAcr. dimerization, hydrogen atom transfer from [H 1 H]+ to MeAcr., and decomposition of [H 1 H]+. MeAcrH was produced in excellent yields through a single‐step H? transfer from [H 1 (NCMe)]+ to MeAcr+, but [H 1 (CO)]+ was inactive toward MeAcr+. 相似文献
10.
《Journal of Coordination Chemistry》2012,65(7):603-610
The title complex [K{Cu(acen)}3]2[Co(NCS)4]·1/4CH3OH (acen = acetylacetonethylenediamine anion) has been prepared and characterized. Single-crystal x-ray analysis reveals that the complex crystallizes in space group P I with a = 11.442(2), b = 15.098(3), c = 28.500(4) Å, α = 82.77(1), β = 83.58(1), γ = 85.07(1)°. The crystal consists of the complex [K{Cu(acen)}3]+ cations, [Co(NCS)4]2? anions and methanol molecules. Three [Cu(acen)] molecules function as bridging ligands through phenolic O atoms to one K+ to give the tetranuclear [K{Cu(acen)}3]+ cation. Each copper(II) atom in the cation is in a square-planar geometry, being coordinated by two oxygen atoms and two nitrogen atoms from a quadridentate acen ligand. The cobalt(II) atom is coordinated by four nitrogen atoms of thiocyanate ligands, forming a deformed tetrahedral environment. The IR and UV-Vis spectra have also been investigated. 相似文献
11.
Ernesto Schulz Lang Prof. Dr. Gelson Manzoni de Oliveira Prof. Dr. Greice Tabarelli 《无机化学与普通化学杂志》2008,634(3):416-418
Selenium and bromine were refluxed in methanol and stirred with ethylenethiourea to give yellow crystals of [(Se‐ettu)2]Br2 (ettu = ethylenethiourea). The first reported 1,2‐diselenonium dication stabilized by sulfur atoms is air unstable and yields a three‐dimensional lattice with Se+···Br?···Se+ bridges enclosing also single Se+···Br? interactions and H···Br? bonds. The air instability of [(Se‐ettu)2]Br2 probably is due to redox reactions which lead to the decomposition of ethylenethiourea with precipitation of sulfur. 相似文献
12.
Hans Bock RodneyF. Claridge Camelia Bogdan Mark Sievert Volker Krenzel 《Helvetica chimica acta》2001,84(6):1227-1242
Redox Reactions of Hexahydropyrene: Crystal Structures of Its Radical‐Anion Salts as well as of Trihydropyrenylium Tetrachloroaluminate and Density‐Functional‐Theory Calculations Hexahydropyrene 1 , a doubly propane‐1,3‐diyl‐bridged peri‐naphthalene derivative wtih 10 π‐electrons allows both oxidation to its cation as well as reduction to its radical‐anion salts, which could be crystallized and structurally characterized – a rather rare case for small unsaturated hydrocarbons. The unexpected formally threefold dehydrogenation by the oxidizing system AlCl3/H2CCl2 (Bock's reagent) generated the hitherto unknown 1,2,3‐trihydropyrene cation in two polymorphic crystals, which contain 12 π‐electrons delocalized over three anellated six‐membered rings comprising 13 π‐centers. Structural comparison of the altogether four crystallized redox products [K+solv][M.−] 2a , [K+solv][M.−]∞ 2b , [Na+solv][M.−] 2c , and [(M−3 H)+][AlCl−4] 3 with the neutral hydrocarbon 1 reveals only small differences in bond lengths and angles, but establishes solvation contacts, π(η6)⋅⋅⋅K+ coordination in the polymer 2b , the flattening of one molecular half in the trihydropyren cation of 3 and ten H‐bonds CH⋅⋅⋅Cl to the AlCl4− counter anion of 3 . DFT/NBO Charge distributions, calculated based on the experimental structural parameters, show charge accumulation in the propanediyl bridges as well as in the peripheral naphthalene C−C bonds of the radical anions. The largest changes result expectedly for the formally triply dehydrogenated 1 , i.e. the trihydropyren cation of 3 , with two slightly positive and partly considerably less negative π‐centers. 相似文献
13.
K2AgIn3Se6 was synthesized by a molten-salt (alkali-metal polyselenide flux) reaction at 500 ℃. The orange red granular crystal crystallizes in monoclinic space group C2/c with cell parameters, a=1.16411(7) nm, b=1.16348(8) nm, c=2.14179(12) nm, V=2.8740(9) nm^3, and Z=8. The crystal has a new two-dimensional structure containing ^2∞[AgIn3Se6]^2- anionic layers separated by K^- cations and the ^2∞[AgIn3Se6]^2- layer is constructed with corner-shared [AgSe4] and [InSe4] tetrahedra. The optical band gap of K2AgIn3Se6 was determined to be ca. 2.9 eV by UV/vis/NIR diffuse reflectance spectra. 相似文献
14.
Philippe Weis Dr. Ian M. Riddlestone Dr. Harald Scherer Prof. Dr. Ingo Krossing 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(52):12159-12168
The complexes Ag(L)n[WCA] (L=P4S3, P4Se3, As4S3, and As4S4; [WCA]=[Al(ORF)4]− and [F{Al(ORF)3}2]−; RF=C(CF3)3; WCA=weakly coordinating anion) were tested for their performance as ligand-transfer reagents to transfer the poorly soluble nortricyclane cages P4S3, P4Se3, and As4S3 as well as realgar As4S4 to different transition-metal fragments. As4S4 and As4S3 with the poorest solubility did not yield complexes. However, the more soluble silver-coordinated P4S3 and P4Se3 cages were transferred to the electron-poor Fp+ moiety ([CpFe(CO)2]+). Thus, reaction of the silver salt in the presence of the ligand with Fp−Br yielded [Fp−P4S3][Al(ORF)4] ( 1 a ), [Fp−P4S3][F(Al(ORF)3)2] ( 1 b ), and [Fp−P4Se3][Al(ORF)4] ( 2 ). Reactions with P4S3 also yielded [FpPPh3−P4S3][Al(ORF)4] ( 3 ), a complex with the more electron-rich monophosphine-substituted Fp+ analogue [FpPPh3]+ ([CpFe(PPh3)(CO)]+). All complex salts were characterized by single-crystal XRD, NMR, Raman, and IR spectroscopy. Interestingly, they show characteristic blueshifts of the vibrational modes of the cage, as well as structural contractions of the cages upon coordination to the Fp/FpPPh3 moieties, which oppose the typically observed cage expansions that lead to redshifts in the spectra. Structure, bonding, and thermodynamics were investigated by DFT calculations, which support the observed cage contractions. Its reason is assigned to σ and π donation from the slightly P−P and P−E antibonding P4E3-cage HOMO (e symmetry) to the metal acceptor fragment. 相似文献
15.
Walter Bauer Jochen Ellermann Martina Dotzler Diana Pohl Frank W. Heinemann Matthias Moll 《无机化学与普通化学杂志》2000,626(2):574-587
Chemistry of Polyfunctional Molecules. 133. X‐Ray Crystal Structural, Solid‐state 31P CP/MAS NMR, TOSS, 31P COSY NMR, and Mechanistic Contributions to the Co‐ordination Chemistry of Octacarbonyldicobalt with the Ligands Bis(diphenylphosphanyl)amine, Bis(diphenylphosphanyl)methane, and 1,1,1‐Tris(diphenylphosphanyl)ethane Co2(CO)8 reacts with bis(diphenylphosphanyl)amine, HN(PPh2)2 (Hdppa, 1 ), in two steps to afford the known compound [Co(CO)(Hdppa‐κ2P)2][Co(CO)4] · 2 THF ( 6 a · 2 THF). The intermediate [Co(CO)2(Hdppa‐κ2P) · (Hdppa‐κP)][Co(CO)4] · dioxane · n‐pentane ( 5 · dioxane · n‐pentane) was isolated for the first time and was characterized by X‐ray analysis. The cation 5 + exhibits a slightly distorted trigonal‐bipyramidal geometry. Detailed 31P‐NMR investigations (solid‐state CP/MAS NMR, TOSS, 31P‐COSY, 31P‐EXSY) showed that the additional tautomer [Co(CO)2(Hdppa‐κ2P)(Ph2P–N=P(H)Ph2‐κP)]+ ( 5 ′+) is present in solution. The tautomer equilibrium is slow in the NMR time scale. In contrast to the solid state only tetragonal pyramidal species of 5 are found in solution. At –90 °C there is slow exchange between the three diastereomeric species 5 a +– 5 c +. Compound 5 forms [Co(CO) · (Hdppa‐κ2P)2]BPh4 · THF ( 6 b · THF) in THF with NaBPh4 under CO‐Elimination. A X‐ray diffraction investigation shows that the cation 6 + consists of a slightly distorted trigonal‐bipyramidal co‐ordination polyeder. However, a distorted tetragonal‐pyramidal structure has been found for the cation 7 + of the related compound [Co(CO)(dppm)2][Co(CO)4] · 2 THF ( 7 · 2 THF; dppm = bis(diphenylphosphanyl)methane, Ph2PCH2PPh2). A comparison with the known [8] trigonal‐bipyramidal stereoisomer, ascertained for 7 + of the solvent‐free 7 , is described. In solutions of 6 a · 2 THF and 7 · 2 THF 13C{1H}‐ and 31P{1H}‐NMR spectra indicate an exchange of all CO and organophosphane molecules between cobalt(I) cation and cobalt(–I) anion. A concerted mechanism for the exchange process is discussed. CO elimination leads to discontinuance of the cyclic mechanism by forming binuclear substitution products such as the isolated Co2(CO)2 · (μ‐CO)2(μ‐dppm)2 · 0.83 THF ( 8 · 0.83 THF), which was characterized by spectroscopy and X‐ray analysis. For the dissolved [Co(CO)2CH3C(CH2PPh2)3][Co(CO)4] · 0.83 n‐pentane ( 9 a · 0.83 n‐pentane) no CO and triphos exchange processes between the cation and the anion are observed. Metathesis of 9 a · 0.83 n‐pentane with NaBPh4 yields [Co(CO)2CH3C(CH2PPh2)3]BPh4 ( 9 b ) which has been characterized by single‐crystal X‐ray analysis. The cation shows a small distorted tetragonal‐pyramidal structure. 相似文献
16.
Quaternary Cesium Copper(I) Lanthanoid(III) Selenides of the Type CsCu3M2Se5 (M = Sm, Gd — Lu) By oxidation of mixtures of copper and lanthanoid metal with elemental selenium in molar ratios of 1 : 1 : 2 and in addition of CsCl quaternary cesium copper(I) lanthanoid(III) selenides with the formula CsCu3M2Se5 (M = Sm, Gd — Lu) were obtained at 750 °C within a week from torch‐sealed evacuated silica tubes. An excess of CsCl as flux helps to crystallize golden yellow or red, needle‐shaped, water‐resistant single crystals. The crystal structure of CsCu3M2Se5 (M = Sm, Gd — Lu) (orthorhombic, Cmcm, Z = 4; e. g. CsCu3Sm2Se5: a = 417.84(3), b = 1470.91(8), c = 1764.78(9) pm and CsCu3Lu2Se5: a = 407.63(3), b = 1464.86(8), c = 1707.21(9) pm, respectively) contains [MSe6]9— octahedra which share edges to form double chains running along [100]. Those are further connected by vertices to generate a two‐dimensional layer parallel to (010). By edge‐ and vertex‐linking of [CuSe4]7— tetrahedra two crystallographically different Cu+ cations build up two‐dimensional puckered layers parallel to (010) as well. These sheet‐like structure interconnects the equation/tex2gif-stack-3.gif{[M2Se5]4—} layers to create a three‐dimensional network according to equation/tex2gif-stack-4.gif{[Cu3M2Se5]—}. Thus empty channels along [100] form, apt to take up the Cs+ cations. These are surrounded by eight plus one Se2— anions in the shape of (2+1)‐fold capped trigonal prisms with Cs—Se distances between 348 and 368 pm (8×) and 437 (for M = Sm) or 440 pm (for M = Lu), respectively, for the ninth ligand. 相似文献
17.
One‐Electron Oxidation of [M(PtBu3)2] (M=Pd,Pt): Isolation of Monomeric [Pd(PtBu3)2]+ and Redox‐Promoted C−H Bond Cyclometalation
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Dr. Thibault Troadec Sze‐yin Tan Dr. Christopher J. Wedge Dr. Jonathan P. Rourke Prof. Dr. Patrick R. Unwin Dr. Adrian B. Chaplin 《Angewandte Chemie (International ed. in English)》2016,55(11):3754-3757
Oxidation of zero‐valent phosphine complexes [M(PtBu3)2] (M=Pd, Pt) has been investigated in 1,2‐difluorobenzene solution using cyclic voltammetry and subsequently using the ferrocenium cation as a chemical redox agent. In the case of palladium, a mononuclear paramagnetic PdI derivative was readily isolated from solution and fully characterized (EPR, X‐ray crystallography). While in situ electrochemical measurements are consistent with initial one‐electron oxidation, the heavier congener undergoes C?H bond cyclometalation and ultimately affords the 14 valence‐electron PtII complex [Pt(κ2PC‐PtBu2CMe2CH2)(PtBu3)]+ with concomitant formation of [Pt(PtBu3)2H]+. 相似文献
18.
Dipl. Chem. Robin Brückner Dipl. Chem. Heike Haller Mathias Ellwanger Dr. Sebastian Riedel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(18):5741-5747
Polychloride monoanions stabilized by quaternary ammonium salts are investigated using Raman spectroscopy and state‐of‐the‐art quantum‐chemical calculations. A regular V‐shaped pentachloride is characterized for the [N(Me)4][Cl5] salt, whereas a hockey‐stick‐like structure is tentatively assigned for [N(Et)4][Cl2???Cl3?]. Increasing the size of the cation to the quaternary ammonium salts [NPr4]+ and [NBu4]+ leads to the formation of the [Cl3]? anion. The latter is found to be a pale yellow liquid at about 40 °C, whereas all the other compounds exist as powders. Further to these observations, the novel [Cl9]? anion is characterized by low‐temperature Raman spectroscopy in conjunction with quantum‐chemical calculations. 相似文献
19.
Thibault Troadec Sze‐yin Tan Christopher J. Wedge Jonathan P. Rourke Patrick R. Unwin Adrian B. Chaplin 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2016,128(11):3818-3821
Oxidation of zero‐valent phosphine complexes [M(PtBu3)2] (M=Pd, Pt) has been investigated in 1,2‐difluorobenzene solution using cyclic voltammetry and subsequently using the ferrocenium cation as a chemical redox agent. In the case of palladium, a mononuclear paramagnetic PdI derivative was readily isolated from solution and fully characterized (EPR, X‐ray crystallography). While in situ electrochemical measurements are consistent with initial one‐electron oxidation, the heavier congener undergoes C−H bond cyclometalation and ultimately affords the 14 valence‐electron PtII complex [Pt(κ2PC‐PtBu2CMe2CH2)(PtBu3)]+ with concomitant formation of [Pt(PtBu3)2H]+. 相似文献
20.
Raphael Seelbinder Dr. Nadine R. Goetz Johannes Weber Dr. Rolf Minkwitz Prof. Dr. Andreas J. Kornath Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(3):1026-1032
Sulfurtrioxide reacts with the superacidic solutions XF/SbF5 (X=H, D) to form the corresponding salts [X2SO3F]+[SbF6]?, which are the protonated forms of fluorosulfuric acid. The salts have been characterized by vibrational spectroscopy and a single‐crystal structure analysis. [H2SO3F]+[SbF6]? crystallizes in the monoclinic space group P21/n (no. 14) with four formula units in the unit cell. The crystal structure possesses a distorted tetrahedral O3SF skeleton of the cations, which are linked with two strong hydrogen bridges to [SbF6]? anions and forms a one‐dimensional chain. The crystal structure and the vibrational spectra are compared to the quantum‐chemical‐calculated free [H2SO3F]+ cation. Additionally, an [H2SO3F(HF)2]+ unit was calculated at the RHF/6‐311++G(d,p) level to simulate H???F hydrogen bridges found in the solid state. 相似文献