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1.
The Effect of the Spacer of Bis(biurea) Ligands on the Structure of A2L3‐type (A=anion) Phosphate Complexes
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Prof. Biao Wu Dr. Shaoguang Li Prof. Yibo Lei Prof. Huaiming Hu Dr. Nader de Sousa Amadeu Prof. Dr. Christoph Janiak Dr. Jennifer S. Mathieson Dr. De‐Liang Long Prof. Leroy Cronin Prof. Xiao‐Juan Yang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2588-2593
By tuning the length and rigidity of the spacer of bis(biurea) ligands L, three structural motifs of the A2L3 complexes (A represents anion, here orthophosphate PO43?), namely helicate, mesocate, and mono‐bridged motif, have been assembled by coordination of the ligand to phosphate anion. Crystal structure analysis indicated that in the three complexes, each of the phosphate ions is coordinated by twelve hydrogen bonds from six surrounding urea groups. The anion coordination properties in solution have also been studied. The results further demonstrate the coordination behavior of phosphate ion, which shows strong tendency for coordination saturation and geometrical preference, thus allowing for the assembly of novel anion coordination‐based structures as in transition‐metal complexes. 相似文献
2.
L. S. Zakharov G. N. Molchanova T. M. Shcherbina P. V. Petrovskii M. I. Kabachnik 《Russian Chemical Bulletin》1998,47(9):1718-1724
A number of trialkylsilylmethyl diphenyl phosphates MeRR′SiCH2OP(O)(OPh)2 (1a-e: R=Et (a), Pr (b), CF3CH2CH2 (c, e), Me3SiCH2 (d); R′=Me (a-d), Et (e)) were synthesized and their thermal rearrangement, of the 1,2-shift type, was studied. The rearrangement consists of the
migration of an alkyl group from Si atom to the methylene carbon atom and gives the corresponding silyl esters. The rate of
the rearrangement was found to increase in the order1d<1b<1a<1 (R=R′=Me)<1c corresponding to the enhancement of the total inductive effect (−I) of the substituents at the Si atom. The relative migration ability of the substituents at the Si atom, determined by GC/MS
analysis of the disiloxane fraction resulting from hydrolysis of pyrolyzed phosphates1a-e, increases in the order R=Pr<Et<CF3CH2CH2<Me≪Me3SiCH2, which differs substantially from the order in which the rate of the rearrangement of phosphates1a-d changes. The electronegativity of the migrating group affects noticeably the relative ability to migrate.
For Part 4, see Ref. 1.
Deceased.
Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 9, pp. 1767–1772, September, 1998. 相似文献
3.
稀土磷酸盐发光材料的微波合成 总被引:5,自引:0,他引:5
稀土磷酸盐发光材料的微波合成徐文国,田一光,刘淼,刘海堂,方光华,庞文琴(吉林大学化学系,环境科学系,长春,130023)关键词微波合成,稀土磷酸盐,微晶玻璃,玻璃态,发光材料稀土磷酸盐发光材料的研究是当前材料科学的热门研究课题。它们一般通过高温固相... 相似文献
4.
Goryunov E. I. Petrovskii P. V. Shcherbina T. M. Zakharov L. S. 《Russian Chemical Bulletin》2001,50(6):1085-1087
Catalytic phosphorylation of -trifluoromethylbenzyl alcohols with POCl3 taken in a ratio of 3 : 1 under particular temperature conditions afforded predominantly symmetrical tris(-trifluoromethylbenzyl) phosphates. The latter were obtained as mixtures of two diastereomers with a statistical ratio of the components. 相似文献
5.
A.?H.?Naik N.?V.?Thakkar S.?R.?DharwadkarEmail author K.?D.?Singh Mudher V.?Venugopal 《Journal of Thermal Analysis and Calorimetry》2004,78(3):707-713
Sodium zirconium phosphate [NaZr2P3O12], a potential ceramic matrix for fixation of high level nuclear waste, was synthesized by heating the mixture of sodium carbonate [Na2CO3], zirconyl nitrate hydrate [ZrO(NO3)2·5H2O] and ammonium dihydrogen phosphate [NH4H2PO4] in air, in a resistance heated furnace and a microwave heating system respectively in the temperature range 450 to 650°C. The mixture heated for 1 h in a resistance furnace at 450°C yielded a poorly crystalline NaZr2P3O12 [NZP]. Increasing the temperature to 650°C produced a highly crystalline product. The same mixture heated in a microwave oven at 450°C for 1 h however, yielded the most crystalline NZP.In an alternate method, the mixture of sodium dihydrogen phosphate (NaH2PO4), zirconium dioxide (ZrO2) and diammonium hydrogen phosphate [(NH4)2HPO4] heated in resistance furnace at 650°C for the same period did not react in air. It also did not yield the pure product at 450°C when heated in microwave assembly for 1 h.The authors thank the Board of Research in Nuclear Sciences (BRNS) of the Department of Atomic Energy (DAE) for the financial support for this work under the project No. 2000/37/19/BRNS/1959 dtd09-02-02. 相似文献
6.
João Paulo R.F. André Hugh D. Burrows Carlos F.G.C. Geraldes Maria Da Graça M. Miguel M.Helena S.F. Teixeira L.F. Vilas Boas 《Polyhedron》1996,15(24):4331-4340
Complexation of europium(III) with glyceryl-1- and -2-phosphates has been studied by metal ion luminescence, 1H and 13C NMR spectroscopy and potentiometry. From the luminescence and NMR studies, the formation of a 1:1 inner-sphere complex, in which the glyceryl phosphate is directly bound to the metal, is confirmed. Similar apparent binding constants at pH 2 were obtained by the three methods. Values obtained by NMR at pH 2 are 53 M−1 and 12 M−1 for glyceryl-1- and -2-phosphate, respectively. By comparison with literature data on related systems it is suggested that the ligands bind through the phosphate group. To obtain structural information from the NMR data, complexation has also been studied with the lanthanide ions Dy(III), Er(III) and Gd(III) using both chemical shift and relaxation data. From this, metal-proton distance ratios have been calculated. Comparison of 1H and 13C NMR spectral data in the presence of paramagnetic lanthanides suggests conformational equilibria in the solutions. From the potentiometric studies, global formation constants have been determined, and speciation diagrams obtained over the pH range 1.5pH7.0 for ligand/metal ratios of 1 and 30. Implications of these results on lanthanide induced fusion of phospholipid membranes are discussed. 相似文献
7.
8.
Binary zirconium orthophosphates R1/3Zr2(PO4)3 and M1/4Zr2(PO4)3, where R = Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu; M = Th, U, have been synthesized and studied by IR spectroscopy [structural family of NaZr2(PO4)3 (NZP)]. Vibrational analysis for the PO4 tetrahedron and investigation of symmetry relations among trigonal NZP phases showed that ordering of lanthanide atoms in structures of NaZr2(PO4)3 type with space group R
c leads to symmetry reduced to P
c. The lanthanide atoms occupy the 2b sites. The phosphorus atoms occupy two independent sites: 6f with C
2 symmetry and 12g with C
1 symmetry. Factor group analysis admits that the IR spectrum can contain eight v3 bands and two v1 bands of the stretching vibrations of the PO4 ions. The M atoms of actinides occupy statistical positions in the structure, and space group R
c is retained.Original Russian Text Copyright © 2004 by V. S. Kurazhkovskaya, D. M. Bykov, and A. I. Orlova__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 6, pp. 1013–1019, November–December, 2004. 相似文献
9.
Santana MD García G Lozano AA López G Tudela J Pérez J García L Lezama L Rojo T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(7):1738-1746
The bis(phosphatediester)-bridged complexes [[Ni([12]aneN(3))(mu-O(2)P(OR)(2))](2)](PF(6))(2) [[12]aneN(3)=Me(3)[12]aneN(3), 2,4,4-trimethyl-1,5,9-triazacyclododec-1-ene; R=Me (1), Bu (2), Ph (3), Ph-4-NO(2) (4); [12]aneN(3)=Me(4)[12]aneN(3), 2,4,4,9-tetramethyl-1,5,9-triazacyclododec-1-ene; R=Me (5), Bu (6), Ph (7), Ph-4-NO(2) (8)] were prepared by hydrolysis of the phosphate triester with the hydroxo complex [[Ni([12]aneN(3))(mu-OH)](2)](PF(6))(2) or by acid-base reaction of the dialkyl or diaryl phosphoric acid and the above hydroxo complex. The acid-base reaction was also used to synthesise the phosphinate-bridged complexes [[Ni([12]aneN(3))(mu-O(2)PR(2))](2)](PF(6))(2) [[12]aneN(3)=Me(3)[12]aneN(3), R=Me (9), Ph (10); [12]aneN(3)=Me(4)[12]aneN(3), R=Me (11), Ph (12)]. The molecular structures of complexes 2, 3 and 12 were established by single crystal X-ray diffraction studies. The eight-membered rings defined by the nickel atoms and the bridging ligands show distorted twist-boat, chair and boat-boat conformations in 2, 3 and 12, respectively. The experimental susceptibility data for compounds 2, 3 and 12 were fitted by least-squares methods to the analytical expression given by Ginsberg. The best fit was obtained with values of J=-0.11 cm(-1), D=-9.5 cm(-1) and g=2.20 for 2; J=-0.97 cm(-1), D=-9.3 cm(-1) and g=2.21 for 3; and J=-0.14 cm(-1), D=-11.9 cm(-1) and g=2.195 for 12. The magnetic-exchange pathways must involve the phosphate/phosphinate bridges, because these favour antiferromagnetic interactions. The observation of a higher exchange parameter for compound 3 is a consequence of a favourable disposition of the O-P-O bridges. The kinetics for the hydrolysis of TNP (tris(4-nitrophenyl)phosphate) with the dinuclear nickel(II) hydroxo complex [[Ni(Me(3)[12]aneN(3))(mu-OH)](2)](PF(6))(2) was studied by UV-visible spectroscopy. The proposed mechanism for TNP-promoted hydrolysis can be described as one-substrate/two-product, and can be fitted to a Michaelis-Menten equation. 相似文献
10.
The conditions of formation of complex lanthanide chromate(VI)-phosphates K2R(CrO4)(PO4) were found and these compounds were synthesized by solid-state synthesis with variation of the starting compounds, the temperature
of synthesis (500–800 °C), and the annealing time (6–200 h). These salts are typical of late lanthanides, R = Dy-Lu, Y. Using
lutetium derivatives as examples, it was shown that no similar compounds with lithium or sodium are formed. All the complex
chromate(VI)-phosphates obtained decompose under static conditions at temperatures above 550 °C. They are isostructural and crystallize
in the monoclinic system. The unit cell parameters for thulium, ytterbium, and lutetium compounds were calculated. It is shown
by IR spectroscopy that PO4 tetrahedra in the crystal lattice of potassium lanthanide chromate(VI)-phosphates are substantially distorted, whereas the CrO4 tetrahedra retain the regular tetrahedron symmetry (T
d
).
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 622–626, April, 2006. 相似文献