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1.
《Journal of Coordination Chemistry》2012,65(11):2028-2033
The new cyclic phosph(V)azane ligand [(C6H5N)P(O)H]2 (2) is obtained from the reaction between PCl3 and PhNH2 in toluene followed by controlled hydrolysis of the product in an H2O–CHCl3 solution. Compound 2 is the first example of P(V) dimer [(µ-NC6H5)P(H)=O]2, a P2N2 ring with two P(O)H moieties. The reaction of 2 with ZnCl2 in a molar ratio of 1?:?1 in tetrahydrofuran yields the cyclophosph(V)azane complex Cl2Zn[(C6H5N)P(O)H]2 (3) in which Zn–O bonds form directly between a cyclic phosph(V)azane ligand and Zn(II). The products have been characterized by infrared, multinuclear (1H, 31P, 13C) NMR, mass spectrometry, and elemental analysis. 相似文献
2.
Karl O. Christe David A. Dixon Mathias Hopfinger Thomas M. Klapötke Burkhard Krumm 《Journal of fluorine chemistry》2010,131(7):791-422
The [((C6H5)3P)2N]+, [(C6H5)4P]+ and [N(CH3)4]+ salts of SeF5−, SeF62− and SeOF3− and CsSeO2F were prepared and characterized. Crystal structures were obtained for [((C6H5)3P)2N][SeF5] and [((C6H5)3P)2N][SeOF3] CH2Cl2. In contrast to oxygen-bridged dimeric TeOF3−, the SeOF3− anion in [((C6H5)3P)2N][SeOF3] CH2Cl2 is monomeric and represents the first experimentally well determined molecular structure of a monomeric trifluoro-chalcogenite anion. Similarly, [((C6H5)3P)2N][SeF5] represents the first example of a structure containing a well-isolated undistorted SeF5− anion. The NMR and the vibrational spectra and their assignments were re-examined and corrected by comparison with high-level theoretical calculations. Whereas the previously published normal coordinate analysis of SeF5− is correct, that for SeOF3− needs major revision. 相似文献
3.
A detailed analysis of the 35Cl/37Cl isotope effects observed in the 19.11 MHz 103Rh NMR resonances of [RhCln(H2O)6−n]3−n complexes (n = 3–6) in acidic solution at 292.1 K, shows that the ‘fine structure’ of each 103Rh resonance can be understood in terms of the unique isotopologue and in certain instances the isotopomer distribution in each complex. These 35Cl/37Cl isotope effects in the 103Rh NMR resonance of the [Rh35/37Cl6]3− species manifest only as a result of the statistically expected 35Cl/37Cl isotopologues, whereas for the aquated species such as for example [Rh35/37Cl5(H2O)]2−, cis-[Rh35/37Cl4(H2O)2]− as well as the mer-[Rh35/37Cl3(H2O)3] complexes, additional fine-structure due to the various possible isotopomers within each class of isotopologues, is visible. Of interest is the possibility of the direct identification of stereoisomers cis-[RhCl4(H2O)2]−, trans-[RhCl4(H2O)2]−, fac-[RhCl3(H2O)3] and mer-[RhCl3(H2O)3] based on the 103Rh NMR line shape, other than on the basis of their very similar δ(103Rh) chemical shift. The 103Rh NMR resonance structure thus serves as a novel and unique ‘NMR-fingerprint’ leading to the unambiguous assignment of [RhCln(H2O)6−n]3−n complexes (n = 3–6), without reliance on accurate δ(103Rh) chemical shifts. 相似文献
4.
Angel García-Raso Juan J. Fiol Andrés Tasada Francisca M. Albertí Ferran Bádenas Xavier Solans Mercè Font-Bardia 《Polyhedron》2007
The reaction of N9,N9′-(tri or tetramethylene)-bisadenines (Ade2Cx; x = 3 or 4) in HCl 2 M at 50 °C with MCl2 · 2H2O [M = Zn(II), Cd(II)] yields outer sphere compounds like the previously described [(H-Ade)2C3][ZnCl4] · H2O (3) and [(H-Ade)2C3]2[Cd2Cl8(H2O)2] · 4H2O (4) for Ade2C3 and the new {[(H-Ade)2C4][Cd2Cl6(H2O)2] · 2H2O}n (5) for Ade2C4. On the other hand, only in case of Zn(II) complexes by changing [HCl] to 0.1 M, the inner sphere compounds [H-(Ade)2C3(ZnCl3)] (6) and [H-(Ade)2C4(ZnCl3)] · 1.5H2O (7) are obtained. X-ray diffraction study of compound 6, which represents the first inner sphere complex with a N9,N9′-bisadenine, shows a zwitterionic form with one adenine ring protonated at N(1) while the other ring is coordinated via N(7) to a ZnCl3 moiety as in other alkyl-adenine derivatives. In addition, with Ade2C4, is also possible to obtain another inner sphere complex: [(H-Ade)2C4(ZnCl3)2] · 3H2O (8). 相似文献
5.
Theocharis C. StamatatosSpyros P. Perlepes Catherine P. RaptopoulouVassilis Psycharis Nikolaos Klouras 《Polyhedron》2011,30(3):451-457
The reactivity pattern of the 16-electron species [M(Cp)2Cl2] (M = Zr, Hf; Cp− = η5-C5H5−) and [Ti(MeCp)2Cl2] (MeCp− = η5-C5H4CH3−) towards the dipicolinate(−2) (dipic2−) ligand under mild (ambient temperature) and convenient (aerobic reactions, aqueous media) conditions have been investigated. The syntheses, molecular structures and spectroscopic (IR, 1H NMR) characterization are reported for the 18-electron products [Zr(Cp)2(dipic)] (1), [Hf(Cp)2(dipic)] (2) and [Ti(MeCp)2(dipic)] (3). The dipic2− ion behaves as N,O,O′-chelating ligand in the three complexes, while the centroids of the Cp− (1, 2) and MeCp− (3) rings formally occupy the fourth and fifth coordination sites about the central metal. The two identical/very similar bite angles of only ∼70° make the dipic2− ligand particularly suited to form stable metallocene derivatives with 5-coordinate geometry. IR and 1H NMR data are discussed in terms of the known structures and the tridentate chelating mode of the dipic2− ligand. 相似文献
6.
The rate-surfactant concentration profiles for the reaction of the insecticide paraoxon with hydroxamate ions (R(CO)·NHO−, R = CH3, R = C6H5, R = 2-HOC6H4) in aqueous solutions of cetyltrimethylammonium salts, CTAX (X− = Br−, Cl−, SO3H−) have been measured at pH 11.0 at 30 °C. All these profiles are typical of micelle-assisted bimolecular reactions involving interfacial ion exchanges. The salicylhydroxymic acid-CTACl combination is most reactive. 相似文献
7.
Dale A. Pennington William Clegg Simon J. Lancaster 《Journal of organometallic chemistry》2006,691(14):3183-3188
Treatment of the mono(salicylaldiminato)titanium complexes {3-But-2-(O)C6H3CHN(Ar)}TiCl3(THF) (Ar = C6H5, 2,4,6-Me3C6H2 or C6F5) with the potassium β-enaminoketonates (C6H5)NC(CH3)C(H)C(R)OK (R = CH3, CF3) yielded the first examples of heteroligated (salicylaldiminato) (β-enaminoketonato)titanium dichloride complexes. The complex {3-But-2-(O)C6H3CHN(C6H5)}{(C6H5)NC(CH3)C(H)C(CH3)O}TiCl2 was structurally characterized by X-ray diffraction and has an orientation with trans-O,O,cis-Cl,Cl, cis-N,N distorted octahedral geometry. These complexes polymerize ethene when activated with MAO; the highest productivity, 5650 kg PE (mol metal)−1 h−1 atm−1, was afforded by {3-But-2-(O)C6H3CHN(C6F5)}{(C6H5)NC(CH3)C(H)C(CF3)O}TiCl2 at 60 °C. 相似文献
8.
The oxonium derivative P(C6H5)4[2-B10H9O(CH2)4] (1) has been prepared from [B10H10]2− by a solvent-addition reaction route, promoted by Et2O · BF3. Its structure has been confirmed by single crystal X-ray analysis. 1 is assumed to be a useful synthon for the derivative chemistry of [B10H10]2−. As an illustration, ring-opening reaction occurred in presence of the strong nucleophilic agent OH−, giving the monoanionic derivative [P(C6H5)4]2[2-B10H9O(CH2)4OH] (2). 相似文献
9.
Two solid phase transitions of [Cd(H2O)6](BF4)2 occurring on heating at TC2=183.3 K and TC1=325.3 K, with 2 K and 5 K hysteresis, respectively, were detected by differential scanning calorimetry (DSC). High value of entropy changes indicated large orientational disorder of the high temperature and intermediate phase. Nuclear magnetic resonance (1H NMR and 19F NMR) relaxation measurements revealed that the phase transitions at TC1 and TC2 were associated with a drastic and small change, respectively, of the both spin-lattice relaxation times: T1(1H) and T1(19F). These relaxation processes were connected with the “tumbling” motions of the [Cd(H2O)6]2+, reorientational motions of the H2O ligands, and with the iso- and anisotropic reorientation of the BF4− anions. The cross-relaxation effect was observed in phase III. The line width and the second moment of the 1H and 19F NMR line measurements revealed that the H2O reorientate in all three phases of the title compound. On heating the onset of the reorientation of 3 H2O in the [Cd(H2O)6]+2, around the three-fold symmetry axis of these octahedron, causes the isotropic reorientation of the whole cation. The BF4− reorientate isotropically in the phases I and II, but in the phase III they perform slow reorientation only about three- or two-fold axes. A small distortion in the structure of BF4− as well as of [Cd(H2O)6]2+ is postulated. The temperature dependence of the bandwidth of the O-H stretching mode measured by Fourier transform middle infrared spectroscopy (FT-MIR) indicated that the activation energy for the reorientation of the H2O did not change much at the TC2 phase transition. 相似文献
10.
Monojit Mitra Anowar Hossain Prankrishna Manna Somnath Ray Choudhury Surasak Kaenket Madeleine Helliwell 《Journal of Coordination Chemistry》2017,70(3):463-474
A Cu(II)-methylmalonate complex, (C3H7N6)4[Cu(II)(C4H4O4)2](H2O)4Cl2 (1) (where C3H7N6 = protonated melamine, C4H4O4 = methylmalonic acid), has been synthesized from aqueous media and its crystal structure was determined by single-crystal X-ray diffraction. The anionic Cu(II)-methylmalonate complex mediated formation of interesting supramolecular assemblies in the solid state by means of ionic interactions with protonated melamine. Moreover, other forces such as antielectrostatic H-bonding and π+–π+ interactions also play a crucial role in defining the final 3-D architecture of 1. An interesting stacking among protonated melamine molecules is studied by DFT calculations. Lattice water molecules and chlorides form various hydrogen bonds to take part in the self-assembly processes. 相似文献
11.
Ching-Feng Fu 《Tetrahedron》2010,66(12):2119-4589
N-Heterocyclic carbenes (NHCs) are known to be useful ligands for palladium-complex catalysis. It was found that [(NHC)Pd(PPh3)Cl2] is an effective pre-catalyst in Pd-catalyzed C-S cross coupling reactions to produce the functionalized sulfides in excellent yields. The turn over frequency (TOF) for the coupling of p-CH3C6H4Br with p-CH3C6H4SH reaches to 6.25 (mol of product) (mole of catalyst)−1 h−1. 相似文献
12.
The low-temperature reaction of [CrCl3(thf)3] with LiC6H3Cl2-2,6 yields the organochromium(III) compound [Li(thf)4][CrIII(C6H3Cl2-2,6)4] (1) in 48% yield. The homoleptic, anionic species [CrIII(C6H3Cl2-2,6)4]− is electrochemically related to the neutral one [CrIV(C6H3Cl2-2,6)4] (2) through a reversible one-electron exchange process (E1/2 = 0.16 V, ΔEp = 0.09 V, ipa/ipc = 1.18). Compound 2 was isolated in 74% yield by chemical oxidation of 1 with [N(C6H4Br-4)3][SbCl6]. Attempts to prepare the salt [NBu4][CrIII(C6Cl5)4] (4) by direct arylation of [CrCl3(thf)3] with LiC6Cl5 in the presence of [NBu4]Br gave the organochromium(II) salt [NBu4]2[CrII(C6Cl5)4] (3) instead, as the result of a reduction process. The salt [NBu4][CrIII(C6Cl5)4] (4) was cleanly prepared by comproportionation of 3 and [CrIV(C6Cl5)4]. The reaction of [MoCl4(dme)] with LiC6Cl5 in Et2O solution proceeded with oxidation of the metal center to give the paramagnetic (S = 1/2), five-coordinate salt [Li(thf)4][MoVO(C6Cl5)4] (5). The crystal and molecular structures of 1 and 2 have been established by X-ray diffraction methods. The magnetic properties of 1 and 4 (S = 3/2) as well as those of 2 (S = 1) have been established by EPR spectroscopy as well as by ac and dc magnetization measurements. 相似文献
13.
Somayyeh Rostamzadehmansor Shahriare Ghammamy Kheyrollah Mehrani 《Journal of fluorine chemistry》2008,129(8):674-679
The reaction of VOF3 with (C2H5)4NF, (CH3)4NCl and (C4H9)4NBr salts in anhydrous CH3CN produced new complexes with the anion general formula [VOF3X]− in that (X = F−, Cl−, Br−). These were characterized by elemental analysis, IR, UV/Visible and 19F NMR spectroscopy. The optimized geometries and frequencies of the stationary point are calculated at the B3LYP/6-311G level of theory. Theoretical results showed that the VX (X = F, Cl, Br) bond length values for the [VOF3X]− in compounds 1-3 are 1.8247, 2.4031 and 2.5595 Å, respectively. Also, the VF5 bond length values in [VOF3X]− are 1.824, 1.812 and 1.802 Å, respectively. These results reveal that the bond order for VX bonds decrease from compounds 1 to 3, while for VF5 bonds, the bond orders increase. It can be concluded that the decrease of VX bonds lengths and the increase of VF5 bond lengths in compounds 1-3 result from the increase of the hyperconjugation from compounds 1 to 3. Harmonic vibrational frequencies and infrared intensities for VOF4−, VOF3Cl− and VOF3Br− are studied by means of theoretical and experimental methods. The calculated frequencies are in reasonable agreement with the experiment values. These data can be used in models of phosphoryl transfer enzymes because vanadate can often bind to phosphoryl transfer enzymes to form a trigonal-bipyramidal structure at the active site. 相似文献
14.
Bei-Ping Liu Zhi-Cheng Tan Xiao-Zheng LanHua-Guang Yu Da-Shun ZhangLi-Xian Sun 《Thermochimica Acta》2003,401(2):233-238
Two solid-state coordination compounds of rare earth metals with glycin, [Gd4/3Y2/3(Gly)6(H2O)4](ClO4)6·5H2O and [ErY(Gly)6(H2O)4](ClO4)6·5H2O were synthesized. The low-temperature heat capacities of the two coordination compounds were measured with an adiabatic calorimeter over the temperature range from 78 to 376 K. [Gd4/3Y2/3(Gly)6(H2O)4](ClO4)6·5H2O melted at 342.90 K, while [ErY(Gly)6(H2O)4](ClO4)6·5H2O melted at 328.79 K. The molar enthalpy and entropy of fusion for the two coordination compounds were determined to be 18.48 kJ mol−1 and 53.9 J K−1 mol−1 for [Gd4/3Y2/3(Gly)6(H2O)4](ClO4)6·5H2O, 1.82 kJ mol−1 and 5.5 J K−1 mol−1 for [ErY(Gly)6(H2O)4](ClO4)6·5H2O, respectively. Thermal decompositions of the two coordination compounds were studied through the thermogravimetry (TG). Possible mechanisms of the decompositions are discussed. 相似文献
15.
The aluminium(III)–citrate complex (NH4)4[Al2(C6H4O7)(C6H5O7)2]·4H2O was characterized using anion exchange chromatography on-line coupled with the element specific ICP-AES detector. Time-dependent monitoring of individual species in aqueous solution at different temperatures gave information about the species stability and the decomposition pathway. The aluminium–citrate complex (NH4)4[Al2(C6H4O7)(C6H5O7)2]·4H2O disintegrated via an unknown intermediary Al(III)–citrate species from which the thermodynamically stable complex [Al3(C6H4O7)3(OH)(H2O)]4− was formed. The activation energy for the decomposition reaction and the pre-exponential factor were determinated to be Ea = 81.95 kJ mol−1 and A = 3.62 × 1013 s−1. 相似文献
16.
The hydration products of 2.5, 5 and 10% Cl− containing metakaolin (MK)-lime pastes are compared with the same obtained from MK-lime paste to understand the chloride binding behaviour of MK during the hydration of cement. Results indicate that 2.5% Cl− addition into the MK-lime paste initially enhances the formation of Friedel's salt (Ca2Al(OH)6Cl·2H2O), but Friedel's salt decomposes at later stages due to the formation of stratlingite (C2ASH8). In 5 and 10% chloride containing pastes, Friedel's salt is observed throughout the reaction periods along with the high amount of CSH. Small amount of stratlingite is also formed on or after 60 day hydration of 5% Cl− containing MK-lime pastes. On the other hand, MK-lime-10% Cl− containing pastes show the complete absence of stratlingite and C4AH13 through out the hydration period, which are the major hydration products of MK-lime paste. Mesuarements of pH of the simulated pore fliuds help to understand the decomposition behaviour of Friedel's salt. From the experimental results, chloride binding mechanism of MK-lime paste is also discussed. 相似文献
17.
Akella Sivaramakrishna 《Journal of organometallic chemistry》2007,692(23):5125-5132
The synthesis, characterization and chemistry of novel η3-allyl metal complexes (M = Ir, Rh) are described. The structures of compounds (C5Me4H)Ir(PPh3)Cl2 (1), (C5Me4H)Ir(PPh3)(η3-1-methylallyl)Br (3a), (C5Me4H)Ir(η4-1,3,5-hexatriene) (8), and (C5Me5)Rh(η3-1-ethylallyl)Br (5d) have been determined by X-ray crystallography. Structural comparisons among these complexes are discussed. It is found that the neutral metal allylic complex [Cp∗IrCl(η3-methylallyl)] (5) ionizes in polar solvents to give [Cp∗Ir(η3-methylallyl)]+Cl− (6) and reaches equilibrium (5 ? 6) at room temperature. Addition of tertiary phosphine ligands to neutral complexes such as [Cp∗Ir(η3-methylallyl)Cl], results in the formation of stable ionic phosphine adducts. Factors such as solvent, length of carbon chain, temperature and light are discussed with respect to the formation, stability and structure of the allyl complexes. 相似文献
18.
The first alkaline earth metal complexes of a dibenzoyl derivative of clodronic acid were prepared and characterised by X-ray crystallography, elemental analysis and infrared spectroscopy. The complexes were [Mg{[Cl2C(PO2O(C(O)C6H5))2](H2O)5} · H2O] (1), [Sr2{[Cl2C(PO2O(C(O)C6H5))2]2(H2O)9} · H2O]n (2) and [Ba{Cl2C(PO2O(C(O)C6H5))2}(H2O)2]n (3). The monomeric units of 1 and the polymeric chains of 2 and 3 form 2D layer-like structures through intermolecular hydrogen bonds. The Cl2C(PO2O(C(O)C6H5))22− ligand acts as a bridging and chelating ligand, forming six- and eight-membered chelate rings with metal atoms. In addition, the previously determined polymeric calcium complex of clodronate, [Ca2{Cl2C(PO3)2}(H2O)6 · 4.5H2O]n(4), was synthesised by hydrolysis method from the dibenzoyl derivative of clodronic acid. 相似文献
19.
Nickel(II) and cobalt(II) complexes with the commercial herbicides 2,4-dichlorophenoxyacetic acid (2,4D; C8H6O3Cl2) and 2-(2,4-dichlorophenoxy)-propionic acid (2,4DP; C9H8O3Cl2) were prepared and characterized. On the basis of the results of elemental analysis and Ni and Co determination, the following
molecular formulae were proposed for the obtained compounds: Ni(C8H5O3Cl2)2·6H2O, Co(C8H5O3Cl2)2·6H2O, Ni(C9H7O3Cl2)2·2H2O and Co(C9H7O3Cl2)2·2H2O. X-ray powder analysis was carried out. The IR, electronic (VIS) spectra and conductivity data were discussed. Water solubility
of the synthesized complexes at room temperature was examined. Thermal decomposition of the compounds was studied. Dehydration
processes occur during heating in air. The anhydrous compounds decompose via different intermediate products to oxides. TG/MS
studies indicate formation of gaseous mass fragments of decomposition including H2O+, OH+, CO2
+, HCl+, Cl2
+, CH3Cl+, CH2O+, C6H6
+ and other.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
20.
This paper presents, a theoretical study of the structural, 13C and 1H NMR chemical shifts, electronic transitions, vibrational analysis, and first hyperpolarizability for Ru(NHC)2Cl2(=CH-p-C6H5) complex in gas phase and different solvents. The solvent effect on structural parameters, frontier orbital energies, Ru=Ccarbene and Ccarbene-H stretching frequencies, and chemical shifts of Ccarbene, CNHC and Hcarbene of complex was explored based on Polarizable Continuum Model (PCM). The wavenumbers of υ(Ru=Ccarbene) and υ(Ccarbene-H) of complex in different solvents were correlated with the Kirkwood–Bauer–Magat equation (KBM). As well as, the polarizability and the first order hyperpolarizability values of the investigated compound were computed in various solvents. 相似文献