Crystal Structure and Vibrational Spectrum of (H2NPPh3)2[SnCl6]·2CH3CN Single crystals of (H2NPPh3)2[SnCl6]·2CH3CN ( 1 ) were obtained by oxidative addition of tin(II) chloride with N‐chloro‐triphenylphosphanimine in acetonitrile in the presence of water. 1 is characterized by IR and Raman spectroscopy as well as by a single crystal structure determination: Space group , Z = 2, lattice dimensions at 193 K: a = 1029.6(1), b = 1441.0(2), c = 1446.1(2) pm, α = 90.91(1)°, β = 92.21(1)°, γ = 92.98(1)°, R1 = 0.0332. 1 forms an ionic structure with two different site positions of the [SnCl6]2? ions. One of them is surrounded by four N‐hydrogen atoms of four (H2NPPh3)+ ions, four CH3CN molecules form N–H···N≡C–CH3 contacts with the other four N‐hydrogen atoms of the cations. Thus, 1 can be written as [(H2NPPh3)4(CH3CN)4(SnCl6)]2+[SnCl6]2?. 相似文献
CASSCF–MRMP2 calculations have been carried out to analyze the reactions of the methyl fluoride molecule with the atomic ions Ge+, As+, Se+ and Sb+. For these interactions, potential energy curves for the low‐lying electronic states were calculated for different approaching modes of the fragments. Particularly, those channels leading to C? H and C? F oxidative addition products, H2FC? M? H+ and H3C? M? F+, respectively were explored, as well as the paths which evolve to the abstraction (M? F++CH3) and the elimination (CH2M++HF) asymptotes. For the reaction Ge++CH3F the only favorable channel leads to fluorine abstraction by the ion. As+ and Sb+ can react with CH3F along pathways yielding stable addition products. However, a viable path joining the oxidative addition product H3C? M? F+ with the elimination asymptote CH2M++HF was found for the reaction of the fluorocarbon compound with As+. No favorable channels were detected for the interaction of fluoromethane with Se+. The results discussed herein allow rationalizing some of the experimental data found for these interactions through gas‐phase mass spectrometry.相似文献
Some new N‐4‐Fluorobenzoyl phosphoric triamides with formula 4‐F‐C6H4C(O)N(H)P(O)X2, X = NH‐C(CH3)3 ( 1 ), NH‐CH2‐CH=CH2 ( 2 ), NH‐CH2C6H5 ( 3 ), N(CH3)(C6H5) ( 4 ), NH‐CH(CH3)(C6H5) ( 5 ) were synthesized and characterized by 1H, 13C, 31P NMR, IR and Mass spectroscopy and elemental analysis. The structures of compounds 1 , 3 and 4 were investigated by X‐ray crystallography. The P=O and C=O bonds in these compounds are anti. Compounds 1 and 3 form one dimensional polymeric chain produced by intra‐ and intermolecular ‐P=O···H‐N‐ hydrogen bonds. Compound 4 forms only a centrosymmetric dimer in the crystalline lattice via two equal ‐P=O···H‐N‐ hydrogen bonds. 1H and 13C NMR spectra show two series of signals for the two amine groups in compound 1 . This is also observed for the two α‐methylbenzylamine groups in 5 due to the presence of chiral carbon atom in molecule. 13C NMR spectrum of compound 4 shows that 2J(P,Caliphatic) coupling constant for CH2 group is greater than for CH3 in agreement with our previous study. Mass spectra of compounds 1 ‐ 3 (containing 4‐F‐C6H4C(O)N(H)P(O) moiety) indicate the fragments of amidophosphoric acid and 4‐F‐C6H4CN+ that formed in a pseudo McLafferty rearrangement pathway. Also, the fragments of aliphatic amines have high intensity in mass spectra. 相似文献
Bis(tetramethylammonium) dodecahydrododecaborate, [(CH3)4N]2[B12H12], and bis(tetramethylammonium) dodecahydrododecaborate acetonitrile, [(CH3)4N]2[B12H12] · CH3CN, were synthesized and characterized via Infrared, 1H and 11B NMR spectroscopy. [(CH3)4N]2[B12H12] crystallizes isopunctual to the alkali metal dodecaborates. The crystal structure of [(CH3)4N]2[B12H12] · CH3CN was determined from single crystal data and refined in the orthorhombic crystal system (Pcmn, no. 62, a = 898.68(8), b = 1312.85(9) c = 1994.5(1) pm, R(|F| , 4σ) = 5.9%, wR(F2) = 18.3%). Here, the geometry of the dodecaborate anion is that of an almost ideal icosahedron, less distorted than most other dodecaborates known. By low‐temperature Guinier‐Simon diffractometry phase transitions were detected for [(CH3)4N]2[B12H12] and [(CH3)4N]2[B12H12] · CH3CN at –70 and –15 °C, respectively. 相似文献
The reaction of Hppko (Hppko = phenyl 2‐pyridyl ketone oxime) and CoCl2 · 6H2O in the CH3OH solvent with the presence of triethylamine (NEt3) at room temperature and the exposure to air resulted in the formation of a new pentanuclear, mixed‐valence cobalt complex with the molecular formula [{CoII(CH3O)3}2{CoIII3(μ3‐O)(ppko)3}Cl2]. X‐ray single crystal analysis displays a trigonal bipyramid configuration with the terminal two CoII ions wrapping an triangle [CoIII3O]7+ core. The intermolecular C–H ··· O and C–H ··· Cl interactions form a 2D network framework. The analysis of magnetic susceptibility revealed the dominant antiferromagnetic interactions and strong orbital contribution of CoII ions. 相似文献
By using molecular beam apparatus the visible (450–900 nm) chemiluminescence of the reaction F + CH3F was investigated. Seven vibronic bands of HCF (Ã1A-XA') and four vibrational bands of HF ground state overtone transitions were obtained. The relative vibrational state distributions of HF (V'=4,5,6) states and the rotational temperature of HF (V'=3) state were obtained. The analyses show that the two kinds of spectra were caused by the secondary reaction F+CH3F. The results may be helpful to explain the contradictory results of the experiments in F+CH3F system. 相似文献
Single crystals of [Be3(μ3‐O)3(MeCN)6{Be(MeCN)3}3](I)6·4CH3CN ( 1 ·4CH3CN) were obtained in low yield by the reaction of beryllium powder with iodine in acetonitrile suspension, which probably result from traces of beryllium oxide containing the applied beryllium metal. The compound 1 ·4CH3CN forms moisture sensitive, colourless crystal needles, which were characterized by IR spectroscopy and X‐ray diffraction (Space group Pnma, Z = 4, lattice dimensions at 100(2) K: a = 2317.4(1), b = 2491.4(1), c = 1190.6(1) pm, R1 = 0.0315). The hexaiodide complex cation 1 6+consists of a cyclo‐Be3O3 core with slightly distorted chair conformation, stabilized by coordination of two acetonitrile ligands at each of the beryllium atoms and by a {Be(CH3CN)3}2+ cation at each of the oxygen atoms. This unique coordination behaviour results in coplanar OBe3 units with short Be–O distances of 155.0 pm and 153.6 pm on average of bond lengths within the cyclo‐Be3O3 unit and of the peripheric BeO bonds, respectively. Exposure of compound 1 ·4CH3CN to moist air leads to small orange crystal plates of [Be(H2O)4]I2·2CH3CN ( 3 ·2CH3CN). According to the crystal structure determination (Space group C2/c, Z = 4, lattice dimensions at 100(2) K: a = 1220.7(1), b = 735.0(1), c = 1608.5(1) pm, β = 97.97(1)°, R1 = 0.0394), all hydrogen atoms of the dication [Be(H2O)4]2+ are involved to form O–H ··· N and O–H ··· I hydrogen bonds with the acetonitrile molecules and the iodide ions, respectively. Quantum chemical calculations (B3LYP/6‐311+G**) at the model [Be3(μ3‐O)3(HCN)6{Be(HCN)3}3]6+ show that chair and boat conformation are stable and that the distorted chair conformation is stabilized by packing effects. 相似文献
Reaction of PF5 · CH3CN with Hydrogensulfide The reaction of PF5 · CH3CN with SH? proceeds with cleavage of the P? F bonds and/or by transformations of the coordinated CH3CN. The following species have been assigned in NMR spectra: of which the first three have been isolated as salts. The course of the reaction is discussed and a comparison is made to the reaction of AsF5 · CH3CN with SH?. 相似文献
[{(CH3)3Si}3C–Li–C{Si(CH3)3}3][Li · 3(OC4H8)] and {(CH3)3Si}3C–Li · O=C(Si(CH3)3)2, two New Adducts of Lithium Trisylmethanide Sublimation of (Tsi–Li) · 2 THF (Tsi = –C(Si(CH3)3)3) at 180 °C and 10–4 hPa gives (Tsi–Li) · 1.5 THF in very low yield. The X‐ray structure determination shows an almost linear [Tsi–Li–Tsi]– anion connected by short agostic Li…C contacts with the threefold THF‐coordinated Li‐cation. Base‐free Tsi–Li, solved in toluene is decomposed by oxygen, forming the strawberry‐colored ketone O=C(SiMe3)2, which forms an 1 : 1 adduct with undecomposed Tsi–Li. The X‐ray structure elucidation of this compound is also discussed. 相似文献