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1.
A one‐dimensional aluminum phosphate, [NH3(CH2)2NH2(CH2)3NH3]3+ [Al(PO4)2]3—, has been synthesized hydrothermally in the presence of N‐(2‐Aminoethyl‐)1, 3‐diaminopropane (AEDAP) and its structure determined by single crystal X‐ray diffraction. Crystal data: space group = Pbca (no. 61), a = 16.850(2), b = 8.832(1), c = 17.688(4)Å, V = 2632.4(2)Å3, Z = 8, R1 = 0.0389 [5663 observed reflections with I > 2σ(I)]. The structure consists of anionic [Al(PO4)2]3— chains built up from AlO4 and PO4 tetrahedra, in which all the AlO4 vertices are shared and each PO4 tetrahedron possesses two terminal P=O linkages. The cations, which balances the negative charge of the chains, are located in between the chains and interact with the oxygen atoms through strong N—H···O hydrogen bonds. Additional characterization of the compound by powder XRD and MAS‐NMR has also been performed and described.  相似文献   

2.
The Crystal Structure of cis‐ and trans‐N‐iso‐Propylamidodimethyl Indium, [(CH3)2In‐N(H)iC3H7]2 According to the X‐ray structure determination [(CH3)2In‐N(H)iC3H7]2 (prepared from InMe3 (Me = CH3) and H2NiPr (iPr = CH(CH3)2) crystallizes in the monoclinic space group P21/n with 3 dimeric trans as well as 3 dimeric cis isomers per unit cell. The centrosymmetric form has a planar In2N2 core with In—N bonds of 222.1(4) and 222.9(5) pm, respectively, the skeleton of the cis isomer with In—N bonds of 221.4(4) pm is slightly folded (13.7°). Some 1H, 13C NMR, IR, and Raman data are reported.  相似文献   

3.
4‐Amino‐trans‐azobenzene {or 4‐[(E)‐phenyl­diazen­yl]aniline} can form isomeric salts depending on the site of protonation. Both orange bis{4‐[(E)‐phenyl­diazen­yl]anilinium} hydrogen phos­phate, 2C12H12N3+·HPO42−, and purple 4‐[(E)‐phenyl­diazen­yl]­anilinium dihydrogen phosphate phosphoric acid solvate, C12H12N3+·H2PO4·H3PO4, (II), have layered structures formed through O—H⋯O and N—H⋯O hydrogen bonds. Additionally, azobenzene fragments in (I) are assembled through C—H⋯π inter­actions and in (II) through π–π inter­actions. Arguments for the colour difference are tentatively proposed.  相似文献   

4.
Pulse radiolysis techniques were used to measure the gas phase UV absorption spectra of the title peroxy radicals over the range 215–340 nm. By scaling to σ(CH3O2)240 nm = (4.24 ± 0.27) × 10?18, the following absorption cross sections were determined: σ(HO2)240 nm = 1.29 ± 0.16, σ(C2H5O2)240 nm = 4.71 ± 0.45, σ(CH3C(O)CH2O2)240 nm = 2.03 ± 0.22, σ(CH3C(O)CH2O2)230 nm = 2.94 ± 0.29, and σ(CH3C(O)CH2O2)310 nm = 1.31 ± 0.15 (base e, units of 10?18 cm2 molecule?1). To support the UV measurements, FTIR‐smog chamber techniques were employed to investigate the reaction of F and Cl atoms with acetone. The F atom reaction proceeds via two channels: the major channel (92% ± 3%) gives CH3C(O)CH2 radicals and HF, while the minor channel (8% ± 1%) gives CH3 radicals and CH3C(O)F. The majority (>97%) of the Cl atom reaction proceeds via H atom abstraction to give CH3C(O)CH2 radicals. The results are discussed with respect to the literature data concerning the UV absorption spectra of CH3C(O)CH2O2 and other peroxy radicals. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 283–291, 2002  相似文献   

5.
Heterobimetallic Complexes of Lithium, Aluminum, and Gold with the N ‐[2‐ N ′, N ′‐(dimethylaminoethyl)‐ N ‐methyl‐aminoethyl]‐ferrocenyl Ligand (η5‐C5H5)Fe{η5‐C5H3[CH(CH3)N(CH3)CH2CH2NMe2]‐2} N‐[2‐N′,N′‐(dimethylaminoethyl)‐N‐methyl‐aminoethyl]ferrocene FcN,NH ( 1 ) reacts with nBuLi under formation of the lithium organyl (FcN,N)Li ( 2 ). At reactions of 2 with AlBr3 and AuCl · PPh3 the heterobimetallic organo derivatives (FcN,N)AlBr2 ( 3 ), (FcN,N)Au · PPh3 ( 4 ) are formed. A detailed characterization of 2 – 4 was carried out by single crystal x‐ray analyses as well as by NMR and Mößbauer spectroscopy.  相似文献   

6.
Electronic structure, charge distributions and vibrational characteristics of CH3 O(CH2 CH2 O) n CH3 (n=3-7) have been derived using the ab initio Hartree Fock and density functional calculations. For tri- to hexaglymes the lowest energy conformers have trans- conformation around the C-C and C-O bonds of the backbone. For heptaglyme (n=7 in the series), however, gauche-conformation around the C-C bonds renders more stability to the conformer and turns out to be 10.1 kJ mol −1 lower in energy relative to the conformer having trans-orientation around the C-C and C-O bonds. The molecular electrostatic potential topographical investigations reveal deeper minima for the ether oxygen in conformers having the gauche conformation around the C-C bonds over those for the trans- conformers. A change from trans- to gauche-conformation around the C-C bonds of the lowest energy conformer of heptaglyme engenders a triplet of intense bands ∼1,150 cm −1 in the vibrational spectra. Theoretical calculations predict that Li + binds strongly to the heptaglyme conformer in the above series. The frequency shifts in the vibrational spectra of CH3O(CH2CH2O) n CH3- Li+ (n=3-7) conformers have been discussed  相似文献   

7.
The structure of the title compound, [Cu2(C12H24N4O2)(C3H4N2)2(CH4O)2](ClO4)2 or [Cu2(dmoxpn)(HIm)2(CH3OH)2](ClO4)2, where dmoxpn is the dianion of N,N′‐bis­[3‐(dimethyl­amino)prop­yl]oxamide and HIm is imidazole, consists of a centrosymmetric trans‐oxamidate‐bridged copper(II) binuclear cation, having an inversion centre at the mid‐point of the central C—C bond, and two perchlorate anions. The CuII atom has square‐pyramidal coordination geometry involving two N atoms and an O atom from the dmoxpn ligand, an N atom from an imidazole ring, and an O atom from a methanol mol­ecule. The crystal structure is stabilized by O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds and imidazole π–π stacking inter­actions to form a three‐dimensional supra­molecular array.  相似文献   

8.
Single crystals of octahedral mer‐cis‐[CoIIII(CH3)2(PMe3)3] ( 1 ) and square planar trans‐[NiIICl(CH3)(PMe3)2] ( 2 ), were obtained from solvent mixtures (methylcylohexane / pentane 1:1) and have been analyzed by X‐ray crystallography for the first time.  相似文献   

9.
The stoichiometric reaction of 1,10‐phenanthroline (phen), imino­di­acetic acid (IDA‐H2) and Cu(ClO4)2 in a H2O–CH3OH (2:1) solution yields μ‐imino­diacetato‐2:1κ4O,N,O′:O′′‐tris(1,10‐phenanthroline)‐1κ4N,N′;2κ2N,N′‐dicopper(II) diperchlorate methanol solvate, [Cu2(C4H5NO4)(C12H8N2)3](ClO4)2·CH3OH. The IDA ligand bridges the two CuII ions via a carboxyl­ate group and uses one further N and an O atom of the second carboxylate group to complete a fac‐tridentate coordination at one Cu centre. A phen ligand completes a distorted square‐pyramidal coordination at this metal atom, although there is weak coordination by a perchlorate O atom at a sixth position. The second Cu centre has a distorted trigonal–bipyramidal coordination to two phen moieties and a carboxyl­ate O atom.  相似文献   

10.
This paper reports on the gas‐phase radical–radical dynamics of the reaction of ground‐state atomic oxygen [O(3P), from the photodissociation of NO2] with secondary isopropyl radicals [(CH3)2CH, from the supersonic flash pyrolysis of isopropyl bromide]. The major reaction channel, O(3P)+(CH3)2CH→C3H6 (propene)+OH, is examined by high‐resolution laser‐induced fluorescence spectroscopy in crossed‐beam configuration. Population analysis shows bimodal nascent rotational distributions of OH (X2Π) products with low‐ and high‐N′′ components in a ratio of 1.25:1. No significant spin–orbit or Λ‐doublet propensities are exhibited in the ground vibrational state. Ab initio computations at the CBS‐QB3 theory level and comparison with prior theory show that the statistical method is not suitable for describing the main reaction channel at the molecular level. Two competing mechanisms are predicted to exist on the lowest doublet potential‐energy surface: direct abstraction, giving the dominant low‐N′′ components, and formation of short‐lived addition complexes that result in hot rotational distributions, giving the high‐N′′ components. The observed competing mechanisms contrast with previous bulk kinetic experiments conducted in a fast‐flow system with photoionization mass spectrometry, which suggested a single abstraction pathway. In addition, comparison of the reactions of O(3P) with primary and tertiary hydrocarbon radicals allows molecular‐level discussion of the reactivity and mechanism of the title reaction.  相似文献   

11.
Smog chamber/Fourier transform infrared (FTIR) techniques were used to measure the kinetics of the reaction of n‐CH3(CH2)xCN (x = 0–3) with Cl atoms and OH radicals: k(CH3CN + Cl) = (1.04 ± 0.25) × 10−14, k(CH3CH2CN + Cl) = (9.20 ± 3.95) × 10−13, k(CH3(CH2)2CN + Cl) = (2.03 ± 0.23) × 10−11, k(CH3(CH2)3CN + Cl) = (6.70 ± 0.67) × 10−11, k(CH3CN + OH) = (4.07 ± 1.21) × 10−14, k(CH3CH2CN + OH) = (1.24 ± 0.27) × 10−13, k(CH3(CH2)2CN + OH) = (4.63 ± 0.99) × 10−13, and k(CH3(CH2)3CN + OH) = (1.58 ± 0.38) × 10−12 cm3 molecule−1 s−1 at a total pressure of 700 Torr of air or N2 diluents at 296 ± 2 K. The atmospheric oxidation of alkyl nitriles proceeds through hydrogen abstraction leading to several carbonyl containing primary oxidation products. HC(O)CN, NCC(O)OONO2, ClC(O)OONO2, and HCN were identified as the main oxidation products from CH3CN, whereas CH3CH2CN gives the products HC(O)CN, CH3C(O)CN, NCC(O)OONO2, and HCN. The oxidation of n‐CH3(CH2)xCN (x = 2–3) leads to a range of oxygenated primary products. Based on the measured OH radical rate constants, the atmospheric lifetimes of n‐CH3(CH2)xCN (x = 0–3) were estimated to be 284, 93, 25, and 7 days for x = 0,1, 2, and 3, respectively.  相似文献   

12.
Reactions of PhAsCl2 with BrMg(CH2)nMgBr (n = 4 or 5) in THF gave phenylarsacycloalkanes as colourless oily liquids which could be distilled under vacuum. Treatment of PhAs(CH2)n­with MCl2(RCN)2 (M = Pd or Pt; R = Ph­or Me) afforded mononuclear complexes, [MCl2{PhAs(CH2)n}2]. Reactions with [Pt2Cl2(μ‐Cl)2(PEt3)2] gave mixed‐ligand complexes, [PtCl2(PEt3){PhAs(CH2)n]. The palladium complexes adopt a trans geometry whereas the platinum complexes exist in a cis configuration. The crystal and molecular structure of [PdCl2(PhAsCH2CH2CH2CH2CH2)2] was determined by X‐ray diffraction methods. The molecule consists of a square‐planar palladium atom with trans chlorides and trans arsa ligands. The six‐membered ‘AsC5′ ring adopts a chair conformation. Copyright © 1999 John Wiley & Sons, Ltd.  相似文献   

13.
The asymmetric unit of the title compound, dipotassium bis[hexaaquanickel(II)] tris(μ2‐methylenediphosphonato)tripalladium(II) hexahydrate, K2[Ni(H2O)6]2[Pd3{CH2(PO3)2}3]·6H2O, consists of half a {[Pd{CH2(PO3)2}]3}6− anion [one Pd atom (4e) and a methylene C atom (4e) occupy positions on a twofold axis] in a rare `handbell‐like' arrangement, with K+ and [Ni(H2O)6]2+ cations to form the neutral complex, completed by three solvent water molecules. The {[Pd{CH2(PO3)2}]3}6− units exhibit close Pd...Pd separations of 3.0469 (4) Å and are packed via intermolecular C—H...Pd hydrogen bonds. The [KO9] and [NiO6] units are assembled into sheets coplanar with (011) and stacked along the [100] direction. Within these sheets there are [K4Ni4O8] and [K2Ni2O4] loops. Successive alternation of the sheets and [Pd{CH2(PO3)2}]3 units parallel to [001] produces the three‐dimensional packing, which is also supported by a dense network of hydrogen bonds involving the solvent water molecules.  相似文献   

14.
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   

15.
Two mixed‐valent disc‐like hepta‐nuclear compounds of [FeIIFeIII6(tea)6](ClO4)2 ( 1Fe , tea = N(CH2CH2O)33?) and [MnII3MnIII4(nmdea)6(N3)6]·CH3OH ( 2Mn , nmdea = CH3N(CH2CH2O)22?) have been synthesized by the reaction of Fe(ClO4)2·6H2O with triethanolamine (H3tea) for the former and reaction of Mn(ClO4)2·6H2O with diethanolamine (H2nmdea) and NaN3 for the later, respectively. 1Fe has the cationic cluster with a planar [FeIIFeIII6] core consisting of one central FeII and six rim FeIII atoms in hexagonal arrangement. The Fe ions are linked by the oxo‐bridges from the alcohol arms in the manner of edge‐sharing of their coordination octahedra. 2Mn is a neutral cluster with a [MnII3MnIII4] core possessing one central MnII atom surrounded by six rim Mn ions, two MnII and four MnIII. The structure is similar to 1Fe but involves six terminal azido ligands, each coordinate one rim Mn ion. 1Fe showed dominant antiferromagnetic interaction within the cluster and long‐range ordering at 2.7 K. The cluster probably has a ground state of low spin of S = 5/2 or 4/2. The long‐range ordering is weak ferromagnetic, showing small hysteresis with a remnant magnetization of 0.3 Nβ and a coercive field of 40 Oe. Moreover, the isofield of lines 1Fe are far from superposition, indicating the presence of significant zero–field splitting. Ferromagnetic interactions are dominant in 2Mn . An intermediate spin ground state 25/2 is observed at low field. In high field of 50 kOe, the energetically lowest state is given by the ms = 31/2 component of the S = 31/2 multiplet due to the Zeeman effect. Despite of the large ground state, no single‐molecule magnet behavior was found above 2 K.  相似文献   

16.
Using four basis bets, (6‐311G(d,p), 6‐31+G(d,p), 6‐31++G(2d,2p), and 6‐311++G(3df,3pd), the optimized structures with all real frequencies were obtained at the MP2 level for the dimers CH2O? HF, CH2O? H2O, CH2O? NH3, and CH2O? CH4. The structures of CH2O? HF, CH2O? H2O, and CH2O? NH3 are cycle‐shaped, which result from the larger bend of σ‐type hydrogen bonds. The bend of σ‐type H‐bond O…H? Y (Y?F, O, N) is illustrated and interpreted by an attractive interaction of a chemically intuitive π‐type hydrogen bond. The π‐type hydrogen bond is the interaction between one of the H atoms of CH2O and lone pair(s) on the F atom in HF, the O atom in H2O, or the N atom in NH3. In contrast with the above three dimers, for CH2O? CH4, because there is not a π‐type hydrogen bond to bend its linear hydrogen bond, the structure of CH2O? CH4 is noncyclic shaped. The interaction energy of hydrogen bonds and the π‐type H‐bond are calculated and discussed at the CCSD (T)/6‐311++G(3df,3pd) level. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005  相似文献   

17.
Using a pulse-radiolysis transient UV–VIS absorption system, rate constants for the reactions of F atoms with CH3CHO (1) and CH3CO radicals with O2 (2) and NO (3) at 295 K and 1000 mbar total pressure of SF6 was determined to be k1=(1.4±0.2)×10−10, k2=(4.4±0.7)×10−12, and k3=(2.4±0.7)×10−11 cm3 molecule−1 s−1. By monitoring the formation of CH3C(O)O2 radicals (λ>250nm) and NO2 (λ=400.5nm) following radiolysis of SF6/CH3CHO/O2 and SF6/CH3CHO/O2/NO mixtures, respectively, it was deduced that reaction of F atoms with CH3CHO gives (65±9)% CH3CO and (35±9)% HC(O)CH2 radicals. Finally, the data obtained here suggest that decomposition of HC(O)CH2O radicals via C C bond scission occurs at a rate of <4.7×105 s−1. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 913–921, 1998  相似文献   

18.
Synthesis and Crystal Structure of the Heterobimetallic Diorganotindichloride (FcN, N)2SnCl2 (FcN, N: (η5‐C5H5)Fe{η5‐C5H3[CH(CH3)N(CH3)CH2CH2NMe2]‐2}) The heterobimetallic title compound [(FcN, N)2SnCl2] ( 1 ) was obtained by the reaction of [LiFcN, N] with SnCl4 in the molar ratio 1:1 in diethylether as a solvent. The two FcN, N ligands in 1 are bound to Sn through a C‐Sn σ‐bond; the amino N atoms of the side‐chain in FcN, N remain uncoordinated. The crystals contain monomeric molecules with a pseudo‐tetrahedral coordination at the Sn atom: Space group P21/c; Z = 4, lattice dimensions at —90 °C: a = 9.6425(2), b = 21.7974(6), c = 18.4365(4) Å, β = 100.809(2)°, R1obs· = 0.051, wR2obs· = 0.136.  相似文献   

19.
A bimolecular rate constant,kDHO, of (29 ± 9) × 10?12 cm3 molecule?1 s?1 was measured using the relative rate technique for the reaction of the hydroxyl radical (OH) with 3,5‐dimethyl‐1‐hexyn‐3‐ol (DHO, HC?CC(OH)(CH3)CH2CH(CH3)2) at (297 ± 3) K and 1 atm total pressure. To more clearly define DHO's indoor environment degradation mechanism, the products of the DHO + OH reaction were also investigated. The positively identified DHO/OH reaction products were acetone ((CH3)2C?O), 3‐butyne‐2‐one (3B2O, HC?CC(?O)(CH3)), 2‐methyl‐propanal (2MP, H(O?)CCH(CH3)2), 4‐methyl‐2‐pentanone (MIBK, CH3C(?O)CH2CH(CH3)2), ethanedial (GLY, HC(?O)C(?O)H), 2‐oxopropanal (MGLY, CH3C(?O)C(?O)H), and 2,3‐butanedione (23BD, CH3C(?O)C(?O)CH3). The yields of 3B2O and MIBK from the DHO/OH reaction were (8.4 ± 0.3) and (26 ± 2)%, respectively. The use of derivatizing agents O‐(2,3,4,5,6‐pentalfluorobenzyl)hydroxylamine (PFBHA) and N,O‐bis(trimethylsilyl)trifluoroacetamide (BSTFA) clearly indicated that several other reaction products were formed. The elucidation of these other reaction products was facilitated by mass spectrometry of the derivatized reaction products coupled with plausible DHO/OH reaction mechanisms based on previously published volatile organic compound/OH gas‐phase reaction mechanisms. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 534–544, 2004  相似文献   

20.
Smog chamber/FTIR techniques were used to study the Cl atom initiated oxidation of CH2FOCH2F in 700 Torr of N2/O2 at 296 K. Relative rate techniques were used to measure k(Cl + CH2FOCH2F) = (4.6 ± 0.7) × 10?13 and k(Cl + CH2FOC(O)F) = (2.9 ± 0.8) × 10?15 (in units of cm3 molecule?1 s?1). Three competing fates for alkoxy radical CH2FOCHFO· formed in the self‐reaction of the corresponding peroxy radicals were identified. In 1 atm of air at 296 K, 48 ± 3% of CH2FOCHFO· radicals decompose via C? O bond scission, 21 ± 4% react with O2, and 31 ± 4% undergo hydrogen atom elimination. Chemical activation effects were observed for CH2FOCHFO· radicals formed in the CH2FOCHFOO· + NO reaction. Infrared spectra of CH2FOC(O)F and FC(O)OC(O)F, which are produced during the Cl atom initiated oxidation of CH2FOCH2F, are presented. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 139–147, 2002; DOI 10.1002/kin.10038  相似文献   

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