氧化铬柱层状铌酸的合成和表征

本文报道先用正丙胺预支撑层状铌酸,然后同氯化四甲铵水溶液进行离子交换,最后再与醋酸铬(Ⅲ)水溶液反应可得含铬(Ⅲ)聚合离子支撑的层状铌酸。进一步焙烧所得含铬(Ⅲ)聚合离子支撑的层状铌酸可得氧化铬柱层状铌酸。该材料具有较高的热稳定性(>700℃)和BET比表面(66.7 m²/g),是一类中等偏弱的新型多孔固体酸(平均孔径为3.3 nm,总酸量为188.3 μmol/g,且主要为Lewis酸)。     

Dimethyl-N-Halogenamine,ihre Ammoniumsalze und Bortrihalogenid-Addukte

Dimethyl-N-Halogenoamine, their Ammonium Salts and Borontrihalide Adducts The preparation and vibrational spectra of (CH₃)₂NHCl⁺X^? (X^? = CF₃SO₃^? I , SO₃F^? II , SO₃Cl^? III , BCl₄^? IV ), and (CH₃)₂NHBr⁺CF₃SO₃^? V as well as the adducts (CH₃)₂NCl · S (S = BF₃ VI , BCl₃ VII , BBr₃ VIII ) and (CH₃)₂NBr · BF₃ IX are reported. The crystal structure of VII has been determined from three-dimensional diffractometer data at ?100°C. The Cl atom and one methyl group in the dimethyl-N-chloroamino group show disorder. The structural data are: B? Cl 183(2) pm, B? N 167(3) pm, N? C 152(3) pm (distances to disordered positions are not included).     

Organic Derivatives of Tin. III. Reactions of Trialkyltin Ethoxide with Alkanolamines

The reactions oi tributyltin ethoxide, Bu₃SnOEt, with N,N-dialkylalkanolamines, HORNR₂ (where R = ? CH₂ · CH₂? , ? CH₂ · CH₂ · CH₂? and ? CH₂ · MeCH? ; R = ? CH₃ and ? C₂H₅) give Bu₃SnORNR₂. In reactions of Bu₃SnOEt with N-methylethanolamine, HOCH₂ · CH₂NHMe, and various alkanolamines, HO · R · NH₂, (where R = ? CH₂ · CH₂? ? CH₂ · CH₂ · CH₂? , ? CHMe · CH₂? ? CH₂ · Me₂C? and ? CH₂ · CH · CH₂ · Me) both the hydroxy as well as the amino groups show reactivity to form products of the type: Bu₃SnOCH₂ · CH₂NHMe, Bu₃SnOCH₂ · CH₂NMeSnBu₃, Bu₃SnO · R · NH₂, Bu₃SnO · R · NHSnBu₃, and Bu₃SnO · R · N(SnBu₃)₂, respectively. The reaction between Bu₃SnOEt and o-aminophenol yields only Bu₃SnO · C₆H₄NH₂.     

A density functional theory study of dimers of hydrophosphoryl compounds and proton transfer in them

The structures of dimers of several types of dimethylphosphinous acid (CH₃)₂POH and dimethylphosphine oxide (CH₃)₂P(O)H and dimers of the corresponding perfluorinated derivatives (CF₃)₂POH and (CF₃)₂P(O)H were studied in detail by density functional theory with the PBE gradient-corrected functional and the TZ2p basis set. Fairly strong dimeric associates (2.50–10.5 kcal/mol) were shown to form thanks to O-H···O, O-H···P, and C-H···O H-bonds and dipole-dipole interactions of polar phosphoryl groups P → O of two monomer molecules. The existence of C-H···O and the absence of P-H···O H-bonds in (CH₃)₂P(O)H dimers was substantiated by an AIM (atoms in molecules) analysis of their structures according to Bader. The reaction coordinates were calculated for synchronous transfer of two protons in (CH₃)₂POH and (CF₃)₂P(O)H dimers. Both rearrangements were shown to occur via symmetrical six-membered planar transition states with activation barriers of less than 20 kcal/mol, which was much lower than for intramolecular transfer in the corresponding monomers (47 kcal/mol for the (CH₃)₂P(O)H → (CH₃)₂POH pair). The tautomeric transitions between the phosphinous acid and phosphine oxide forms observed experimentally in nonpolar media under mild conditions in the absence of molecules that could act as proton carriers were shown to proceed as bimolecular reactions with the intermediate formation of the corresponding dimers.     

Thermodynamic data for hydrogen bonding of thiols with Lewis bases in carbon tetrachloride. Weak association by the PMR method

Data for 30 hydrogen bonding pairs taken from the alkanethiols, i-C₃H₇SH, nC₃H₉SH and t-C₄H₉SH, and 16 bases have been obtained by a PMR method. Representative data for i-C₃H₇SH at 304 ± 2°K are (base, 10²K in M^?1, –ΔH° in kcal/mole): (CH₂)₄S, 3·1, 0·8; (CH₃)₂S, 3·0, 0·9; (CH₃)₂S₂, 3·7, 0·5; (CH₃)₂CO, 4·7, 0·9; CH₃COOC₂H₅, 5·7, 1·1; (CH₂)₄O, 6·1, 1·0; HCON(CH₃)₂, 12, 0·9; (CH₃ O)₂ SO, 12, 0·9; (C₂ H₅O)₃PO, 6·5, 1·0; CH₃ (CH₃ O)₂PO, 18, 1·0; ((CH₃)₂N)₂ CO, 5·9, 1·1; CH₃ CN, 13, 0·6. In essence, the problems and errors involved in obtaining equilibrium data for weak complexes stem from the limited concentration rangethat is accessible. This leads to large uncertainties in the quantities K, ΔH° and ΔS°. Structural effects on hydrogen bonding at the sulfur site, both as Lewis acid or base, are discussed. Two erroneous PMR methods in the literature used for assessing the strength of hydrogen bonds are pointed out.     

Addukte aus Phosphorylverbindungen und SbCl5 Darstellung und IR-Spektren der 1:1-Addukte aus Chlordimethylamino- bzw. Chlordimethylamino-methoxi-phosphorylverbindungen und Antimon(V)-chlorid

Adducts of Phosphoryl Compounds and SbCl₅ Preparation and IR Spectra of 1:1 Addition Compounds from Chlorodimethylamino- resp. Chlorodimethylaminomethoxiphosphoryl Compounds and Antimony(V) Chloride The addition compounds (CH₃O)₂[(CH₃)₂N]PO · SbCl₅ ( II ), (CH₃O)[(CH₃)₂N]₂PO · SbCl₅ ( III ), [(CH₃)₂N]₃PO · SbCl₅ ( IV ), Cl₂[(CH₃)₂N]PO · SbCl₅ ( VI ), Cl[(CH₃)₂N]₂PO · SbCl₅ ( VII ), and Cl(CH₃O)[(CH₃)₂N]PO · SbCl₅ ( VIII ) are prepared by reaction of the phosphoryl compounds with antimony(V) chloride. The influence of the Lewis acid to the bonds of the phosphoryl compounds is discussed. The ³¹P-n.m.r. data of the adducts are communicated and compared with those of the free phosphoryl compounds.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. XL. Über Lithium-alkenylmanganate(II)

Contributions to the Chemistry of Transition Metal Alkyl Compounds. XL. About Lithium Alkenylmanganates(II) MnCl₂ reacts with vinyl, 2,2-dimethylvinyl, allyl, and methallyl lithium giving rise to alkenyl manganates(II). In a pure state the compounds Li₂[Mn(CH?CH₂)₄] · 1.5 diox, Li₂[Mn(CH?C(CH₃)₂)₄] · 1.5 diox, Li₂[Mn(CH₂? CH?CH₂)₄] · 2.5 diox and Li₃[Mn(CH₂? C(CH₃)?CH₂)₅] · 2 diox were isolated. The compounds were characterized by elementary analysis, EPR and IR spectra, magnetic moments, and reactions with iodine.     

Copper(II), Cobalt(II), and Nickel(II) Complexes of two Novel Pyridine‐derived Macrocyclic Ligands bearing o‐ and pNitrobenzyl Pendant Groups

The pendant‐armed ligands L¹ and L² were synthesized by N‐alkylation of the four secondary amine groups of the macrocyclic precursor L using o‐nitrobenzylbromide (L¹) and p‐nitrobenzylbromide (L²). Nitrates and perchlorates of Cu^II, Ni^II and Co^II were used to synthesize the metal complexes of both ligands and the complexes were characterized by microanalysis, MS‐FAB, conductivity measurements, IR and UV‐Vis spectroscopy and magnetic studies. The crystal structures of L¹, [CuL¹](ClO₄)₂·CH₃CN·H₂O, [CuL²](ClO₄)₂·6CH₃CN, [CuL²][Cu(NO₃)₄]·5CH₃CN·0.5CH₃OH and [NiL²](ClO₄)₂·3CH₃CN·H₂O were determined by single crystal X‐ray crystallography. These structural analysis reveal the free ligand L¹, three mononuclear endomacrocyclic complexes {[CuL¹](ClO₄)₂·CH₃CN·H₂O, [CuL²](ClO₄)₂·6CH₃CN and [NiL²](ClO₄)₂·3CH₃CN·H₂O} and one binuclear complex {[CuL²][Cu(NO₃)₄]·5CH₃CN·0.5CH₃OH} in which one of the metals is in the macrocyclic framework and the other metal is outside the ligand cavity and coordinated to four nitrate ions.     

Über Eigenschaften und Reaktivität von Aluminiumtrichlorid · Ethanthiol und Galliumtrichlorid · Ethanthiol

On Some Properties and the Reactivity of Trichloroaluminium · Ethanthiol and Trichlorogallium · Ethanthiol Complexes The synthesis of aluminiumtrichloride · ethanthiol as well as galliumtrichloride · ethanthiol is given. The reactions of these 1:1-adducts with the Lewis bases N(CH₃)₃. P(CH₃)₃, O(C₂H₅)₂ and S(CH₃)₂ and with the compounds (CH₃)₃SiSCH₃ and Pb(SCH₃)₂ are discussed, the reaction products are investigated. Spectra as well as some chemical and physical properties of the starting material and the products are reported.     

Organic solvent effect on the solution-solid phase equilibria in the systems CuCl<Subscript>2</Subscript>-L-H<Subscript>2</Subscript>O (L = DMSO,DMF, acetonitrile) at 25°C

A solution-solid equilibrium in ternary water-organic systems CuCl₂-L-H₂O (L = dimethyl sulfoxide, N,N-dimethyl formamide, and acetonitrile) at 25°C was studied. The expansion of crystallization branches of individual solvates CuCl₂·xL varies in parallel to the donor power of organic solvents. The existence of the mixed crystal-solvates CuCl₂·2H₂O·2(CH₃)₂SO, CuCl₂·2H₂O·2(CH₃)₂NCHO, CuCl₂·H₂O·(CH₃)₂NCHO, CuCl₂·2H₂O·CH₃CN, and CuCl₂·3H₂O·2CH₃CN in the studied systems was proved. Various donor power of oxygen-containing solvents determines the composition of the first coordination sphere of the copper ion in the specified compounds: the coordination of the both solvents in the mixed crystal-solvates with DMF and the absence of water in the nearest environment of the copper(II) ions in the CuCl₂·2H₂O·2(CH₃)₂SO compound.     

Reaktionen von MoNCl3 und WNCl3 mit elementarem Fluor. Kristallstrukturen von [MoO2F2(THF)2] und [WF4(NCl)(CH3CN)]

Reactions of MoNCl₃ and WNCl₃ with Elemental Fluorine. Crystal Structures of [MoO₂F₂(THF)₂] and [WF₄(NCl)(CH₃CN)] The nitrido chlorides MoNCl₃ and WNCl₃ as well as WCl₄(NCl) react with elemental fluorine forming the N-chloro imido complexes MoF₄(NCl) and WF₄(NCl), which were characterized by IR spectroscopy. With tetrahydrofurane MoF₄(NCl) reacts to give [MoF₄(NCl)(THF)], which in THF solution slowly converts into [MoO₂F₂(THF)₂]. From WF₄(NCl) with acetonitrile the complex [WF₄(NCl)(CH₃CN)] is obtained. Both donor acceptor complexes were characterized by crystal structure determinations. [MoO₂F₂(THF)₂] : Space group P2₁/n, Z = 4, structure solution with 1823 unique reflections, R = 0.033 for reflections with I > 2σ(I). Lattice dimensions at ?40°C: a = 636.2, b = 1119.5, c = 1625.2 pm; β = 93.92(1)º. The compound has a monomeric molecular structure with the fluorine atoms in trans-position to one another and with the oxygen atoms of the THF molecules in trans to the oxo ligands. [WF₄(NCl)(CH₃CN)] : Space group P2₁/m, Z = 2, structure solution with 1119 unique reflections, R = 0.038 for reflections with I > 2σ(I). Lattice dimensions at 20°C: a = 511.7, b = 714.9, c = 1002.5 pm; β = 102.59(10)º. The compound has a monomeric molecular structure in which the nitrogen atom of the acetonitrile molecule coordinates in trans-position to the N-chloro imido group W?N? Cl. The structural parameters of this group are WN = 172.2 pm, NCl = 161.1 pm, WNCl = 178.6º.     

Extraction and isolation of the One-electron Oxidized [(Zr6Be)Cl18]5− and [(Zr6Be)Cl18]4− Clusters from solid state precursors

One-electron oxidized zirconium chloride clusters were obtained from solid state precursors Rb₅Zr₆Cl₁₈B and K₃Zr₆Cl₁₅Be by dissolution in CH₃CN in the presence of Et₄NCl and isolated as the salts (Et₄N)₄Zr₆Cl₁₈B · 2 CH₃CN and (Et₄N)₅Zr₆Cl₁₈Be · 3 CH₃CN. (Et₄N)₄Zr₆Cl₁₈B · 2 CH₃CN crystallizes in the space group P1 (#2) with a = 12.329(5) Å, b = 12.657(6) Å, c = 13.136(8) Å, α = 118.28(4)°, β = 93.45(4)°, γ = 105.54(3)°, V = 1696(2) ų, and Z = 1. (Et₄N)₅Zr₆Cl₁₈Be · 3 CH₃CN was refined in the space group C2/c (# 15) with a = 24.166(11) Å, b = 13.265(6) Å, c = 25.86(2) Å, β = 104.21(4)°, V = 8037(7) ų, and Z = 4; the space group reflects the pseudo-symmetry of the crystal, the true symmetry of the structure is lower. The removal of one electron from the Zr? Zr bonding HOMO of both clusters results in cluster expansion of similar magnitude in both compounds. Moisture from the added Et₄NCl is the likely oxidant, but the possibility that acetonitrile may be reduced by [(Zr₆Be)Cl₁₈]^6? is not ruled out.     

Darstellung von Dimethyl-N-Chlorammoniumtrifluormethansulfonat ((CH3)2NClH+ CF3SO3−)

Synthesis of Dimethyl-N-Chloroammonium Trifluoromethane Sulfonate ((CH₃)₂NClH⁺ CF₃SO₃^?) The weak base dimethyl-N-chloroamine, (CH₃)₂NCl, reacts with trifluormethane sulfonic acid at ?40 to ?30°C to give dimethyl-N-chloroammonium trifluoromethane sulfonate (CH₃)₂NClH⁺CF₃SO₃^?. The extremely hygroscopic salt decomposes upon melting at 107 to 108°C and thus is slightly more stable than the hydrogensulfate. Water or methanole liberate dimethyl-N-chloroamine from the salt. The salt is insoluble in ether and decomposes after dissolving in methylene chloride to give dimethylammonium trifluoromethane sulfonate (CH₃)₂NH₂⁺CF₃SO₃^?.     

The distonic ion ·CH2CH2CH+OH,keto ion CH3CH2CH=O +·, enol ion CH3CH=CHOH+·, and related C3H6O+· radical cations. Stabilities and isomerization proclivities studied by dissociation and neutralization-reionization

Metastable ion decompositions, collision-activated dissociation (CAD), and neutralization-reionization mass spectrometry are utilized to study the unimolecular chemistry of distonic ion ^·CH₂CH₂CH^?OH (2^+·) and its enol-keto tautomers CH₃CH=CHOH^?· (1 ^+·) and CH₃CH₂CH=O ^+· (3^+·). The major fragmentation of metastable 1^+·–3^+· is H^· loss to yield the propanoyl cation, CH₃CH₂C≡O⁺. This reaction remains dominant upon collisional activation, although now some isomeric CH₂=CH-CH⁺ OH is coproduced from all three precursors. The CAD and neutralization-reionization (⁺NR⁺) spectra of keto ion 3 ^+· are substantially different from those of tautomers 2^+· and 1^+·. Hence, 3^+· without sufficient energy for decomposition (i. e. , “stable” 3^+·) does not isomerize to the ther-modynamically more stable ions 2^+· or 1^+·, and the 1,4-H rearrangement H-CH₂CH₂CH=O^+·(3 ^+·) → CH₂CH₂CH⁺ O-H (2 ^+·) must require an appreciable critical energy. Although the fragment ion abundances in the ⁺ NR ⁺ (and CAD) spectra of 1 ^+· and 2 ^+· are similar, the relative and absolute intensities of the survivor ions (recovered C₃H₆O^+· ions in the ⁺NR⁺ spectra) are markedly distinct and independent of the internal energy of 1 ^+· and 2 ^+·. Furthermore, 1 ^+· and 2 ^+· show different MI spectra. Based on these data, distonic ion 2 ^+· does not spontaneously rearrange to enol ion 1 ^+· (which is the most stable C₃H₆O^+· of CCCO connectivity) and, therefore, is separated from it by an appreciable barrier. In contrast, the molecular ions of cyclopropanol (4 ^+·) and allyl alcohol (5 ^+·) isomerize readily to 2 ^+·, via ring opening and 1,2-H^? shift, respectively. The sample found to generate the purest 2 ^+· is α-hydroxy-γ-butyrolactone. Several other precursors that would yield 2 ^+· by a least-motion reaction cogenerate detectable quantities of enol ion 1 ^+·, or the enol ion of acetone (CH₂=C(CH₃)OH^+·, 6 ^+·), or methyl vinyl ether ion (CH₃OCH=CH ₂ ^+· , 7 ^+·). Ion 6 ^+· is coproduced from samples that contain the —CH₂—CH(OH)—CH₂— substructure, whereas 7 ^+· is coproduced from compounds with methoxy substituents. Compared to CAD, metastable ion characteristics combined with neutralization-reionization allow for a superior differentiation of the ions studied.     

Unconventional H‐bonds: SH···N interaction

Quantum calculations at the MP2/aug‐cc‐pVDZ level are used to analyze the SH···N H‐bond in complexes pairing H₂S and SH radical with NH₃, N(CH₃)₃, NH₂NH₂, and NH₂N(CH₃)₂. Complexes form nearly linear H‐bonds in which the S? H covalent bond elongates and shifts its stretching frequency to the red. Binding energies vary from 14 kJ/mol for acceptor NH₃ to a maximum of 22 kJ/mol for N(CH₃)₃ and N(CH₃)₂NH₂. Analysis of geometric, vibrational, and electronic data indicate that the SH···N interaction involving SH is slightly stronger than that in which the closed‐shell H₂S serves as donor. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Thermal decomposition of di-t-butyl peroxide in the presence of (CH3)2CCH2: Reactions of CH3, (CH3)2ĊCH2CH3, and (CH3)2ĊCH2C(CH3)2CH2CH3 radicals

A study of the reaction initiated by the thermal decomposition of di-t-butyl peroxide (DTBP) in the presence of (CH₃)₂C?CH₂ (B) at 391–444 K has yielded kinetic data on a number of reactions involving CH₃ (M·), (CH₃)₂CCH₂CH₃ (MB·) and (CH₃)₂?CH₂C(CH₃)₂CH₂CH₃ (MBB·) radicals. The cross-combination ratio for M· and MB· radicals, rate constants for the addition to B of M· and MB· radicals relative to those for their recombination reactions, and rate constants for the decomposition of DTBP, have been determined. The values are, respectively, where θ = RT ln 10 and the units are dm^3/2 mol^?1/2 s^?1/2 for k₂/k and k₉/k, s^?1 for k₀, and kJ mol^?1 for E. Various disproportionation-combination ratios involving M·, MB·, and MBB· radicals have been evaluated. The values obtained are: Δ₁(M·, MB·) = 0.79 ± 0.35, Δ₁(MB·, MB·) = 3.0 ± 1.0, Δ₁(MBB·, MB·) = 0.7 ± 0.4, Δ₁(M·, MBB·) = 4.1 ± 1.0, Δ₁(MB·, MBB·) = 6.2 ± 1.4, and Δ₁(MBB·, MBB·) = 3.9 ± 2.3, where Δ₁ refers to H-abstraction from the CH₃ group adjacent to the center of the second radical, yielding a 1-olefin. © 1994 John Wiley & Sons, Inc.     

Investigation and mechanistic study into intramolecular hydroalkoxylation of unactivated alkenols catalyzed by cationic lanthanide complexes

Cationic lanthanide complexes of the type [Ln(CH₃CN)₉]³⁺[(AlCl₄)₃]^3–·CH₃CN (Ln = Pr, Nd, Sm, Gd, Er, Yb, Y) served as effective catalysts for the intramolecular hydroalkoxylation/cyclization of unactivated alkenols to yield the cyclic ethers with Markovnikov regioselectivity under mild conditions. Novel cationic complexes, [AlCl(CH₃CN)₅]²⁺[(AlCl₄)₂]^2–·CH₃CN and [Nd(CH₃CN)₉]³⁺[(FeCl₄)₃]^3–·CH₃CN, were synthesized and evaluated for the intramolecular hydroalkoxylation/cyclization of unactivated alkenols for comparison. The active sequence of [Nd(CH₃CN)₉]³⁺[(FeCl₄)₃]^3–·CH₃CN < [AlCl(CH₃CN)₅]²⁺[(AlCl₄)₂]^2–·CH₃CN < [Nd(CH₃CN)₉]³⁺[(AlCl₄)₃]^3–·CH₃CN observed indicated that both the cation and anion have great influence on the activity. Comparative study on the activity of AlCl₃ and its cationic complex [AlCl(CH₃CN)₅]²⁺[(AlCl₄)₂]^2–·CH₃CN revealed the formation of the cationic Al center enhanced the activity greatly. The ¹H NMR studies indicated the activation of hydroxyl and olefin by the cationic Ln³⁺ center were involved in the reaction pathways.     

Poly(hydrogen Fluorides) with the Tetramethylammonium Cation: Preparation,Stability Ranges,Crystal Structures, [HnFn+1]− Anion Homology,Hydrogen Bonding F-H…︁F [2]

The melting diagram of the system (CH₃)₄NF? HF was studied between 50 and 100 mole-% HF and from ?185°C to the respective liquidus temperatures (at most 162°C) by difference thermal analysis aided by temperature-dependent X-ray powder diffraction. The system was found to be quasi-binary with the HF-rich intermediary stable compounds (CH₃)₄NF · 2 HF (melting point 110°C), (CH₃)₄NF · 3 HF (20°C, decomposition), (CH₃)₄NF · 5 HF (?76°C, decomposition), and (CH₃)₄NF · 7 HF (?110°C, decomposition), most of which undergo solid-solid phase transitions. Crystal structures were determined of the low-temperature form of (CH₃)₄NF · 2 HF (stable below 83°C, orthorhombic, space group Pbca, Z = 8 formula units per unit cell), the high-temperature form of (CH₃)₄NF · 3 HF (stable above ?87°C, monoclinic, P2/c, Z = 4), and of (CH₃)₄NF · 5 HF (tetragonal, I4 , Z = 2). The structures are those of poly(hydrogen fluorides) (CH₃)₄N[H_nF_n+1] with homologous anions [H₂F₃]^?, [H₃F₄]^?, and [H₅F₆]^?, respectively, formed by strong hydrogen bonding F? H…?F. The anion [H₅F₆]^? is the first one of this composition established by crystal structure analysis. Its structure can be written as [(FH)₂FHF(HF)₂]^? with four equivalent terminal hydrogen bonds of 248.4 pm and a very short central one of 226.6 pm (F…?F distances) through a 4 point of the space group.     

Precipitation temperature of poly(ethylene glycol) in some electrolyte solutions

The effect of sodium fluoride, sodium bromide, tetramethyl ammonium chloride, tetramethyl ammonium bromide and sodium formate on both precipitation and θ-temperatures of poly(ethylene glycol) (M_w = 4000) in aqueous solution have been determined. Curves have been drawn to represent the effect of such ions on both the θ and the precipitation temperatures of the polymer. The effectiveness increases in the order (CH₃)₄ NBr, NaBr, (CH₃)₄NCl, NaF and HCOONa. The M_w-temperatures obtained at infinite dilution are 445 K for NaBr, NaF, (CH₃)₄ NBr and (CH₃)₄NCl and 415 K for HCOONa.     

35Cl Nqr spectroscopy of the [PO2Cl2]− and POCl3 groups in Me(PO2Cl2)2·2D (Me = Mg,Ca, Mn; D = POCl3,CH3COOC2H5,CH3COCH3)

³⁵Cl NQR spectra of dichlorophosphates Me(PO₂Cl₂)₂ · 2D (Me = Mg, Ca, Mn; D = CH₃COOC₂H₅, CH₃COCH₃, POCl₃) are studied in the temperature range 77 ? T (K) ? 305. It is shown that the three compounds with CH₃COOC₂H₅ as donor are isomorphic at 77 K, the crystal structure of Mn(PO₂Cl₂)₂· 2CH₃COOC₂H₅. The structure of Mg(PO₂Cl₂)_2^?· 2CH₃COCH₃ and of Mg(PO₂Cl₂)₂ · 2POCl₃ probably consists of infinite chains as found for Mn(PO₂Cl₂)₂· 2CH₃COOC₂H₅. Mg(PO₂Cl₂)₂· 2CH₃COOC₂H₅ shows phase transformations and a complicated dynamical behaviour leading to strong deviations from a Bayertype NQR function v = f(T). The donor capacity of POCl₃ in Mg(PO₂Cl₂)₂· 2POCl₃ is comparable with the donor strength in AsCl₃ · POCl₃ · A d_π-p_π overlap of the P-O bond influences the P-Cl bond.