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1.
Contributions to the Chemistry of Phosphorus. 239. On the Reaction of Diphosphane(4) with Diborane(6) and with THF-Borane: Formation of Diphosphane-borane, P2H4 · BH3, and Diphosphane-1,2-bis(borane), BH3 · P2H4 · BH3 Diphosphane(4) always reacts with diborane(6) in the temperature range of ?118 to ?78°C, to furnish a mixture of diphosphane-borane, P2H4 · BH3 ( 1 ), and diphosphane-1,2-bis(borane), BH3 · P2H4 · BH3 ( 2 ), in addition to small amounts of triphosphane-1,3-bis(borane), BH3 · P3H5 · BH3, and phosphane-borane, BH3 · PH3, irrespective of the molar ratios of the reactants employed. The formation of the 1 : 1 adduct P2H4 · B2H6 reported in the literature [4] could not be confirmed. The structures of compounds 1 and 2 were investigated by nuclear magnetic resonance spectroscopy which revealed the complete, homolytic cleavage of diborane(6). As a result of the bonding of one BH3 group to diphosphane(4), the Lewis basicity of the other PH2 group is markedly reduced. Similar mixtures of products are obtained when the borane adduct THF · BH3 is employed in an analogous reaction. In the case of a 1 : 1 molar ratio of P2H4 : THF · BH3 at ?78°C, the reaction furnishes compound 1 exclusively. This product can be isolated in the pure state and is found to be appreciably more stable than diphosphane(4). 相似文献
2.
Contributions to the Chemistry of Phosphorus. 241. On the Reaction of Diphosphane(4) with Liquid Ammonia and with Amines – a New Route to Polyphosphides and Hydrogen Polyphosphides Diphosphane(4), P2H4, reacts with liquid ammonia in the temperature range –76 °C to –40 °C to furnish a mixture of the ammonium polyphosphides (NH4)2H2P14, (NH4)2P16, (NH4)3P19, and (NH4)3P21, in addition to PH3. The first intermediate product detectable by NMR spectroscopy is the bicyclic compound NH4H4P7, which reacts further with P2H4 to afford the more phosphorus‐rich polycyclic phosphides. On removal of the ammonia the hydrogen polyphosphide (NH4)2H2P14 decomposes with formation of PH3 and hydrogen‐free, more phosphorus‐rich polyphosphides. When the reaction of diphosphane(4) with liquid ammonia is performed in the presence of tetrahydrofuran the final products are the hydrogen polyphosphides NH4H4P7 and NH4H5P8 together with PH3; the hydrogen‐rich, open‐chain heptaphosphide NH4H8P7 has been identified as a precursor. An investigation of the behavior of diphosphane(4) towards amines using the primary amine ethylenediamine as an example at +10 °C in the absence of a solvent or in the presence of tetrahydrofuran resulted in the formation of a polyphosphide mixture consisting of (C2H4N2H5)2P16, (C2H4N2H5)3P21, and (C2H4N2H5)3P19 as well as some PH3. No reaction occurred with the secondary and tertiary amines diethylamine and tetramethylethylenediamine (TMEDA), respectively, even at room temperature. 相似文献
3.
Contributions to the Chemistry of Phosphorus. 240. On the Reactive Behaviour of Diphosphane-borane, P2H4 · BH3 Under mild temperature conditions, the thermal decomposition of diphosphane-borane ( 1 ) gives rise to the formation of phosphane-borane, PH3 · BH3, and triphosphane-2-borane, PH2? PH(BH3)? PH2 ( 2 ). In the presence of diphosphane-1,2-bis(borane), triphosphane-1,3-bis(borane), BH3? PH2? PH? PH2? BH3 ( 3 ), is formed additionally. The thermolysis product at room temperature is a polymeric solid of varying composition which contains phosphorus, boron, and hydrogen. Compound 1 reacts with metalating agents such as n-BuLi, LiBH4, and NaBH4 to furnish the borane-trihydrogendiphosphide ion, [PH2? PH? BH3]?, which immediately disproportionates to give the corresponding mono-and triphosphane derivatives. In the presence of an excess of THF-borane and in the case of a 1 : 1 molar ratio of 1 : NaBH4, the disproportionation does not occur and the new diphosphide derivative sodium-1,1,2-tris(borane)-1,2,2-trihydrogendiphosphide, Na[(BH3)2PH? PH2BH3] ( 4 ) can be obtained. The action of additional NaBH4 yields the diphosphide dianion with four coordinated BH3 groups. 相似文献
4.
Monophosphane (PH3), diphosphane (P2H4), and triphosphane-5 (P3H5) could be separated in mixtures by isothermal gas chromatography. On the basis of the experiences hereby obtained, further gas chromatographic separations were carried out with a programmed temperature mode. For the identification of the chromatographic peaks a mass spectrometer as a second detector was applied. In the temperature range from ?60°C to +60°C, it was possible for the first time to separate mixtures of diphosphane and higher phosphanes without any decomposition in the gas chromatographic column. Besides monophosphane and diphosphane, triphosphane-3 (P3H3), triphosphane-5 (P3H5), and tetraphosphane-6 (P4H6) could be eluated as undecomposed components. By this, a fundamental basis for the application of gas chromatography to the quantitative analysis of mixtures of phosphanes and to the development of a gas chromatographic method for the preparative isolation of individual higher phosphanes has been established. 相似文献
5.
Contributions to the Chemistry of Phosphorus. 237. On the Reaction of Diphosphane(4) with Peroxo Compounds: Formation of Phosphinophosphinic Acid, H2PPH(O)OH, and Bis(phosphino)phosphinic Acid, (H2P)2P(O)OH Diphosphane(4) reacts with peroxo compounds such as hydrogen peroxide, tetraline hydroperoxide, trifluoroperoxyacetic acid, and cumene hydroperoxide (which is particularly suited for preparative work) at ?30°C to furnish phosphino-phosphinic acid, H2PPH(O)OH ( 1 ), as the primary product. Compound 1 disproportionates to a major extent in statu nascendi to give phosphanes (above all PH3) and monophosphorus acids of various oxidation states as well as some bis(phosphino)phosphinic acid, (H2P)2P(O)OH ( 2 ). The acids 1 and 2 can be trapped and stabilized as their triethylammonium salts. The structures of these salts have been determined by spectroscopic investigations. 相似文献
6.
Concentrated aqueous solutions of magnesium chloride and calcium nitrate, respectively, allow on addition of the potassium salt of tetrathiosquarate, K2C4S4 · H2O, the isolation of the earth alkaline salts MgC4S4 · 6 H2O ( 1 ) and CaC4S4 · 4 H2O ( 2 ) as orange and red crystals. The crystal structure determinations ( 1 : monoclinic, C2/c, a = 17.2280(7), b = 5.9185(2), c = 13.1480(4) Å, β = 104.730(3)°, Z = 4; 2 : monoclinic, P21/m, a = 7.8515(3), b = 12.7705(5), c = 10.6010(4) Å, β = 93.228(2)°, Z = 4) show the presence of C4S42? ions with almost undistorted D4h symmetry having average C–C and C–S bond lengths of 1.451Å and 1.659Å for 1 and 1.451Å and 1.655Å for 2 . The structure of 1 contains discrete, octahedral [Mg(H2O)6]2+ complexes. Several O–H····O and O–H····S bridges with H····O and H····S distances of less than 2.50Å connect cations and anions. The structure of 2 is built of concatenated, edge‐sharing Ca(H2O)6S2 polyhedra. The Ca2+ ions have the coordination number eight, C4S42? act as a chelating ligands towards Ca2+ with Ca–S distances of 3.14Å. The infrared and Raman spectra show bands typical for the molecular building units of the two compounds. 相似文献
7.
M. Baudler H. Stndeke M. Borgardt H. Strabel J. Dobbers H. Muntenbeck Ch. P. Schner W. Faber U. M. Krause W. Kronenberg 《无机化学与普通化学杂志》1995,621(7):1133-1139
Contributions to the Chemistry of Phosphorus. 235. On the Preparation of Larger Amounts of Diphosphane(4) in the Laboratory The preparation of several hundred grammes of diphosphane(4) by hydrolysis of calcium phosphide in a semicontinuous process as well as the handling of larger amounts of this compound are reported. In comparison with earlier results [12], the yield has been raised by 37 percent with simultaneous increase of the accessible total amount. The white solid which is formed in the preparation and purification of diphosphane(4) is not, as was believed in earlier work [25, 8], triphosphane(5) or another, novel phosphorus hydride but is rather a clathrate compound of diphosphane(4) or the phosphanes PnHn+2 (n = 2–4) and water, respectively. 相似文献
8.
H. Worzala 《无机化学与普通化学杂志》1978,445(1):27-35
Crystal Structure of Lead Cyclotetraphosphate-2-Hydrate, Pb2P4O12 · 2H2O By heating of Pb2P4O12 · 4 H2O crystals at 100°C, Pb2P4O12 · 2 H2O is formed topotactically. The triclinic crystals are twinned on (010). Space group: P1 , unit cell: a = 8.02 ± 0.02, b = 10.58 ± 0.02, c = 7.53 ± 0.02 Å, α = 98.8 ± 0.2, β = 108.7 ± 0.2, γ = 82.6 ± 0.3°. The crystal structure was determined by Patterson and Fourier methods and refined by least-squares calculations. The structure consists of two crystallographically different P4O124? ring anions, point symmetry 1 , connected by Pb and hydrogen bonds. Both Pb atoms are coordinated by eight oxygen atoms. The polyhedra of either Pb are interconnected by common edges forming sheets and chains. Pb(1) is joined with four, Pb(2) with five P4O124? anions. 相似文献
9.
Hydrates of Weak and Strong Bases. XI. The Crystal Structures of NaOH · 3,5H2O and NaOH · 7 H2O. A Refinement The crystal structures of the hydrates NaOH · 3,5 H2O (space group P21/c, Z = 8 formula units per unit cell; lattice parameters: a = 6.481, b = 12.460, c = 11.681 Å, β = 104.12° at ?100°C) and NaOH · 7 H2O (P21/c, Z = 4; a = 7.344, b = 16.356, c = 6.897 Å, β = 92.91° at ?150°C) have been redetermined using MoKα diffractometer data. The obtained refinement of the structures, including the localization also of the H atoms for the first time, has led to new findings with respect to the H bonds. In particular, in both hydrates there is one such interaction of the rare type OH? …? OH2, from an OH? ion to an H2O molecule, i. e. with the OH? ion as the proton donor. 相似文献
10.
Diana Pohl Jochen Ellermann Matthias Moll Falk A. Knoch Walter Bauer 《无机化学与普通化学杂志》1996,622(2):283-291
Chemistry of Polyfunctional Molecules. 119 [1]. Tetracarbonyl-dicobalt-tetrahedrane Complexes with the Ligands Bis(diphenylphosphanyl)-amine, 2-Butin-1,4-diol, and tert.-Butylphosphaacetylene — Crystal Structure of the Phosphaalkyne Derivative Co2(μ-CO)2(CO)4(μ-Ph2P? NH? PPh2—P,P′) · 1/2C6H5CH3 ( 4 · 1/2C6H5CH3) reacts with 2-butine-1,4-diol, HOCH2? C?C? CH2OH ( 5 ), to the dark-red tetrahedrane complex Co2(CO)4(μ-η2,η2-HOCH2? C?C? CH2OH? C2, C3) · (μ-Ph2P? NH? PPh2? P,P′) · THF (6 · THF). With t-butyl-phosphaacetylene, tBu? C?P ( 7 ), 4 · THF forms Co2(CO)4(μ-η2,η2-tBu? C?P)(μ-Ph2P? NH? PPh2? P,P′) ( 8 ), which also belongs to the tetrahydrane type. The compounds were characterized by their mass, IR, 31P{1H} NMR, 13C{1H} NMR, and1H NMR spectra. Crystals suitable for X-ray structure analyses have been obtained for 8 from dioxane. The dark red blocks crystallize in the monoclinic P21/c space group with the lattice constants a = 1404,1(5), b = 1330,0(7), c = 2578,8(10)pm; β = 90,82(3)°. 相似文献
11.
L-脯氨酸独有的亚胺基使其在生物医药领域具有许多独特的功能,并广泛用作不对称有机化合物合成的有效催化剂。本文在碱性介质中研究了二(氢过碘酸)合银(III)配离子氧化 L-脯氨酸的反应。经质谱鉴定,脯氨酸氧化后的产物为脯氨酸脱羧生成的 γ-氨基丁酸盐;氧化反应对脯氨酸及Ag(III) 均为一级;二级速率常数 k′ 随 [IO4-] 浓度增加而减小,而与 [OHˉ] 的浓度几乎无关;推测反应机理应包括 [Ag(HIO6)2]5-与 [Ag(HIO6)(H2O)(OH)]2-之间的前期平衡,两种Ag(III)配离子均作为反应的活性组分,在速控步被完全去质子化的脯氨酸平行地还原,两速控步对应的活化参数为: k1 (25 oC)=1.87±0.04(mol·L-1)-1s-1,∆ H1≠=45±4 kJ · mol-1, ∆ S1≠=-90±13 J· K-1·mol-1 and k2 (25 oC) =3.2±0.5(mol·L-1)-1s-1, ∆ H2≠=34±2 kJ · mol-1, ∆ S2≠=-122 ±10 J· K-1·mol-1。本文第一次发现 [Ag(HIO6)2]5-配离子也具有氧化反应活性。 相似文献
12.
The new hexathiodiphosphate(IV) hydrates K4[P2S6] · 4 H2O ( 1 ), Rb4[P2S6] · 6 H2O ( 2 ), and Cs4[P2S6] · 6 H2O ( 3 ) were synthesized by soft chemistry reactions from aqueous solutions of Na4[P2S6] · 6 H2O and the corresponding heavy alkali‐metal hydroxides. Their crystal structures were determined by single crystal X‐ray diffraction. K4[P2S6] · 4 H2O ( 1 ) crystallizes in the monoclinic space group P 21/n with a = 803.7(1), b = 1129.2(1), c = 896.6(1) pm, β = 94.09(1)°, Z = 2. Rb4[P2S6] · 6 H2O ( 2 ) crystallizes in the monoclinic space group P 21/c with a = 909.4(2), b = 1276.6(2), c = 914.9(2) pm, β = 114.34(2)°, Z = 2. Cs4[P2S6] · 6 H2O ( 3 ) crystallizes in the triclinic space group with a = 742.9(2), b = 929.8(2), c = 936.8(2) pm, α = 95.65(2), β = 112.87(2), γ = 112.77(2)°, Z = 1. The structures are built up by discrete [P2S6]4? anions in staggered conformation, the corresponding alkali‐metal cations and water molecules. O ··· S and O ··· O hydrogen bonds between the [P2S6]4? anions and the water molecules consolidate the structures into a three‐dimensional network. The different water‐content compositions result by the corresponding alkali‐metal coordination polyhedra and by the prefered number of water molecules in their coordination sphere, respectively. The FT‐Raman and FT‐IR/FIR spectra of the title compounds have been recorded and interpreted, especially with respect to the [P2S6]4? group. The thermogravimetric analysis showed that K4[P2S6] · 4 H2O converted to K4[P2S6] as it was heated at 100 °C. 相似文献
13.
Polythermal Curves of the Quinary System Na+, K+, Mg2+/Cl?, SO//H2O in Range between +25°C and ?10°C Proceeding from the 0°C, ?5°C and ?10°C isothermal curves of the quinary system Na+, K+, Mg2+/C1?, SO//H2O with saturation at NaCl, KCl, and carnallite, respectively, the polythermal curve is represented between 25°C and ?10°C. Within the new defined range of the polythermal curve the invariant five-salt-paragenesis NaCI, KCI, Glauber's salt (Na2SO4 · 10 H2O), bitter salt (MgSO4 · 7 H2O), Schoenite (K2SO4 · MgSO4 · 6 H2O) can be found at ?7,2°C. It represents also the lowest temperature of formation of Schoenite in this system. It was necessary, moreover, to reconsider further univariant and invariant equilibrium solutions in the range between 25° and 0°C. 相似文献
14.
V2O3(OH)4(g), Proof of Existence, Thermochemical Characterization, and Chemical Vapor Transport Calculations for V2O5(s) in the Presence of Water By use of the Knudsen-cell mass spectrometry the existence of V2O3(OH)4(g) is shown. For the molecules V2O3(OH)4(g), V4O10(g), and V4O8(g) thermodynamic properties were calculated by known Literatur data. The influence of V2O3(OH)4(g) for chemical vapor transport reactions of V2O5(s) with water ist discussed. ΔBH°(V2O3(OH)4(g), 298) = –1920 kJ · mol–1 and S°(V2O3(OH)4(g), 298) = 557 J · K–1 · mol–1, ΔBH°(V4O10(g), 298) = –2865,6 kJ · mol–1 and S°(V4O10(g), 298) = 323.7 J · K–1 · mol–1, ΔBH°(V4O8(g), 298) = –2465 kJ · mol–1 and S°(V4O8(g), 298) = 360 J · K–1 · mol–1. 相似文献
15.
Prof. Dr. Thomas M. Klapötke Jörg Stierstorfer Prof. Dr. H. Donald Brooke Jenkins Rudi van Eldik Matthias Schmeisser 《无机化学与普通化学杂志》2011,637(10):1308-1313
This paper estimates some thermochemical (in kcal mol–1) and detonation parameters for the ionic liquid, [emim][ClO4] and its associated solid in view of its investigation as an energetic material. The thermochemical values estimated, employing CBS‐4M computational methodology and volume‐based thermodynamics (VBT) include: lattice energy, UPOT([emim][ClO4]) ≈? 123 ± 16 kcal · mol–1; enthalpy of formation of the gaseous cation, ΔfH°([emim]+, g) = 144.2 kcal · mol–1 and anion, ΔfH°([ClO4]–, g) = –66.1 kcal · mol–1; the enthalpy of formation of the solid salt, ΔfH°([emim][ClO4],s) ≈? –55 ± 16 kcal · mol–1 and for the associated ionic liquid, ΔfHo([emim][ClO4],l) = –52 ± 16 kcal · mol–1 as well as the corresponding Gibbs energy terms: ΔfG°([emim][ClO4],s) ≈? +29 ± 16 kcal · mol–1 and ΔfGo([emim][ClO4],l) = +24 ± 16 kcal · mol–1 and the associated standard absolute entropies, of the solid [emim][ClO4], S°298([emim][ClO4],s) = 83 ± 4 cal · K–1 · mol–1. The following combustion and detonation parameters are assigned to [emim][ClO4] in its (ionic) liquid form: specific impulse (Isp) = 228 s (monopropellant), detonation velocity (VoD) = 5466 m · s–1, detonation pressure (pC–J) = 99 kbar, explosion temperature (Tex) = 2842 K. 相似文献
16.
The Crystal Structures of [Cu2Cl2(AA · H+)2](NO3)2 and [AA · H+]Picr? (AA · H+ = Allylammonium; Picr? = Picrat) By an alternating current electro synthesis the crystal-line π-complex [Cu2Cl2(AA · H+)2](NO3)2 has been obtained from CuCl2 · 2H2O, allylamine (AA), and HNO3 in ethanolic solution. X-ray structure analysis revealed that the compound crystallized in the monoclinic system, space group P21/a, a = 7.229(3), b = 7.824(3), c = 26.098(6) Å, γ = 94.46(5)°, Z = 4, R = 0.025 for 2 023 reflections. The crystal structure is built up of CunCln chains which are connected by π-bonding bidentate AA · H+ …? ON(O)O …? H+ · AA units. For comparision with the above complex the structure of [AA · H+]Picr? (Picr? = picrate anion) is also reported. 相似文献
17.
On Chalcogenolates. 93. Studies on Trithioallophanic Acid 2. Preparation and Properties of the Free Acid Yellow trithioallophanic acid H2N? CS? NH? CS(SH) has been prepared by reaction between a suspension of K[S2C? NH? CS? NH2] in diethyl ether and a solution of HCl in (C2H5)2O at ?15°C; the ether was distilled off at ?15°C in vacuo. The compound has been characterized by means of infrared spectra, electron absorption, 1H-NMR spectra, and mass spectra. The dissociation constant of trithioallophanic acid in water is Ka = (1,41 ± 0,08) · 10?2 at 20°C. 相似文献
18.
A coordination compound of erbium perchlorate with L-α-glutamic acid, [Er2(Glu)2(H2O)6](ClO4)4·6H2O(s), was synthesized. By chemical analysis, elemental analysis, FTIR, TG/DTG, and comparison with relevant literatures, its chemical composition and structure were established. The mechanism of thermal decomposition of the complex was deduced on the basis of the TG/DTG analysis. Low-temperature heat capacities were measured by a precision automated adiabatic calorimeter from 78 to 318 K. An endothermic peak in the heat capacity curve was observed over the temperature region of 290-318 K, which was ascribed to a solid-to-solid phase transition. The temperature Ttrans, the enthalpy △transHm and the entropy △transSm of the phase transition for the compound were determined to be: (308.73±0.45) K, (10.49±0.05) kJ·mol^-1 and (33.9±0.2) J·K^-1·mol^-1. Polynomial equation of heat capacities as a function of the temperature in the region of 78-290 K was fitted by the least square method. Standard molar enthalpies of dissolution of the mixture [2ErCl3·6H2O(s)+2L-Glu(s)+6NaClO4·H2O(s)] and the mixture {[Er2(Glu)2(H2O)6](ClO4)4·6H2O(s)+6NaCl(s)} in 100 mL of 2 mol·dm^-3 HClO4 as calorimetric solvent, and {2HClO4(1)} in the solution A' at T=298.15 K were measured to be, △dHm,1=(31.552±0.026) kJ·mol^-1, △dHm,2 = (41.302±0.034) kJ·mol^-1, and △dHm,3 = ( 14.986 ± 0.064) kJ·mol^-1, respectively. In accordance with Hess law, the standard molar enthalpy of formation of the complex was determined as △fHm-=-(7551.0±2.4) kJ·mol^-1 by using an isoperibol solution-reaction calorimeter and designing a thermochemical cycle. 相似文献
19.
The complexes of 4-chloro-2-methoxybenzoic acid anion with Mn2+,
Co2+, Ni2+, Cu2+
and Zn2+ were obtained as polycrystalline solids
with general formula M(C8H6ClO3)2·nH2O and colours typical for M(II) ions (Mn – slightly pink, Co –
pink, Ni – slightly green, Cu – turquoise and Zn – white).
The results of elemental, thermal and spectral analyses suggest that compounds
of Mn(II), Cu(II) and Zn(II) are tetrahydrates whereas those of Co(II) and
Ni(II) are pentahydrates. The carboxylate groups in these complexes are monodentate.
The hydrates of 4-chloro-2-methoxybenzoates of Mn(II), Co(II), Ni(II), Cu(II)
and Zn(II) heated in air to 1273 K are dehydrated in one step in the range
of 323–411 K and form anhydrous salts which next in the range of 433–1212
K are decomposed to the following oxides: Mn3O4,
CoO, NiO and ZnO. The final products of decomposition of Cu(II) complex are
CuO and Cu. The solubility value in water at 293 K for all complexes is in
the order of 10–3 mol dm–3.
The plots of χM
vs.
temperature of 4-chloro-2-methoxybenzoates of Mn(II), Co(II), Ni(II) and Cu(II)
follow the Curie–Weiss law. The magnetic moment values of Mn2+,
Co2+, Ni2+ and Cu2+
ions in these complexes were determined in the range of 76−303 K and
they change from: 5.88–6.04 μB for Mn(C8H6ClO3)2·4H2O, 3.96–4.75
μB for Co(C8H6ClO3)2·5H2O, 2.32–3.02 μB for Ni(C8H6ClO3)2·5H2O and 1.77–1.94
μB for Cu(C8H6ClO3)2·4H2O. 相似文献