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1.
E. V. Starodubtseva O. V. Turova M. G. Vinogradov L. S. Gorshkova V. A. Ferapontov 《Russian Chemical Bulletin》2005,54(10):2374-2378
The rate of hydrogenation of γ-ketoesters MeCOCH2CH2COOR (R = Et, Pri, But) in the presence of the chiral RuII—BINAP catalyst (BINAP is 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl) greatly increases upon the addition of 5–10 equivalents
of HCl with respect to ruthenium. In the hydrogenation of ethyl levulinate, the optically active γ-hydroxy ester initially
formed would cyclize by ∼95% to give γ-valerolactone with optical purity of 98–99% ee. When the Ru(COD)(MA)2—BINAP—HCl catalytic system is used (COD is 1,5-cyclooctadiene, MA is 2-methylallyl), complete conversion of the ketoester
(R = Et) in EtOH is attained in 5 h at 60 °C under an H2 pressure of 60–70 atm.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2301–2304, October, 2005. 相似文献
2.
Jian-Long Xia Wei-Cheng Xiong Gang Chen Guang-Ao Yu Shan Jin Sheng-Hua Liu 《Transition Metal Chemistry》2009,34(4):389-393
Abstract Formal [2 + 2 + 2] addition reaction of [Cp*Ru(H2O)(NBD)][BF4] (NBD = norbornadiene) with 4,4′-Diethynylbiphenyl generates [C9H9-η6-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BF4]2. The reaction of [Cp*Ru(H2O)(NBD)][BF4] with 1,4-diphenylbutadiyne generates the unusual [2 + 2 + 2] additional organic compound Ph–C≡C–C9H8–Ph in addition to the organometallic compound [Cp*Ru(η6-C6H5–C≡C–C≡C–Ph)][BF4]. [C9H9-η6-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BPh4]2 is generated after the reaction of compound [C9H9-η6-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BF4]2 with Na[BPh4]. The structure of this compound was confirmed by X-ray diffraction. A possible approach to form Ph–C≡C–C9H8–Ph and [Cp*Ru(η6-C6H5–C≡C–C≡C–Ph)][BF4] is suggested.
Graphical Abstract Formal [2 + 2 + 2] addition reaction of [Cp*Ru(H2O)(NBD)]BF4 (NBD = norbornadiene) with 4,4′-Diethynylbiphenyl generates [C9H9-η6-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BF4]2. The reaction of [Cp*Ru(H2O)(NBD)][BF4] with 1,4-diphenylbutadiyne simply generates unusual [2 + 2 + 2] additional organic compound Ph–C≡C–C9H8–Ph in addition to the organometallic compound [Cp*Ru(η6-C6H5–C≡C–C≡C–Ph)][BF4]. [C9H9-η6-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BPh4]2 is generated after the reaction of compound [C9H9-η6-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BF4]2 with Na[BPh4]. The structure of this compound was confirmed by X-ray diffraction. And the possible approach to form Ph–C≡C–C9H8–Ph and [Cp*Ru(η6-C6H5–C≡C–C≡C–Ph)][BF4] was suggested.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
3.
Prithwiraj Byabartta 《Transition Metal Chemistry》2005,30(7):804-813
Ag+ assisted aquation of blue cis-trans-cis-RuCl2(RaaiR′)2 (4–6) leads to the synthesis of solvento species, blue-violet cis-trans-cis-[Ru(OH2)2(RaaiR′)2](ClO4)2 [Raai R′=p-R-C6H4
N=N–C3H2–NN–1–R′, (1–3), abbreviated as N,N′-chelator, where N(imidazole) and N(azo) represent N and N′, respectively; R = H (a), OMe (b), NO2 (c) and R′ = Me (1/4/7/10), CH2CH3 (2/5/8/11), CH2Ph (3/6/9/12)] that have been reacted with NO2−in warm EtOH resulting in violet dinitro complexes of the type, Ru(NO2)2(RaaiR′)2 (7–9). The nitrite complexes are useful synthons of electrophilic nitrosyls, and on triturating the compounds, (7b–9b) with conc. HClO4 nitro-nitrosyl derivatives, [Ru(NO2)(NO)(OMeaaiR′)2](ClO4)2 (10b–12b) are isolated. The solution structure and stereoretentive transformation in each step have been established from 1H n.m.r. results. All the complexes exhibit strong MLCT transitions in the visible region. They are redox active and display
one metal-centred oxidation and successive ligand-based reductions. The redox potentials of Ru(III)/Ru(II) (E1/2M) of (10b–12b) are anodically shifted by ∼
∼0.2 V as compared to those of dinitro precursors, (7b–9b). The ν(NO) >1900 cm−1 strongly suggests the presence of linear Ru–NO bonding. The electrophilic behaviour of metal bound nitrosyl has been proved
in one case (12b) by reacting with a bicyclic ketone, camphor, containing an active methylene group and an arylhydrazone with an active methine
group, and the heteroleptic tris chelates thus formed have been characterised. 相似文献
4.
Nizam M. El-Ashgar Issa M. El-Nahhal Mohamed M. Chehimi Michel Delamar Florence Babonneau Jacques Livage 《Journal of Sol-Gel Science and Technology》2007,41(1):3-10
A new insoluble solid functionalized ligand system bearing chelating ligand group of the general formula P-(CH2)3-N[CH2CONH(C6H4)NH2]2, where P represents [Si–O]
n
polysiloxane network, was prepared by the reaction of the immobilized diethyliminodiacetate polysiloxane ligand system, P-(CH2)3N(CH2CO2Et)2 with 1,2-diaminobenzene in toluene. 13C CP-MAS NMR, XPS and FTIR results showed that most ethylacetate groups (–COOEt) were converted into the amide groups (–N–C=O).
The new functionalized ligand system exhibits high capacity for extraction and removal of the metal ions (Fe3+, Co2+, Ni2+, Cu2+ and Zn2+) with efficiency of 95–97% after recovery from its primary metal complexes. This functionalized ligand system formed 1:1
metal to ligand complexes. 相似文献
5.
Complexes of CrIII, MnII, ZnII & CdII with the polydentate carboxamide ligandN′, N′′-bis(3-carboxy-1-oxoprop-2-enyl) 2-Amino-N-arylbenzamidine (H2L) have been synthesized and characterized by elemental analyses, spectroscopic studies (Vibrational, electronic, ESR and
1H-NMR), magnetic susceptibility measurements, thermal studies and powder diffraction studies. The vibrational spectral data
are in agreement with coordination of amide and carboxylate oxygen of the ligands with the metal ions. The electronic spectra
indicates octahedral or tetrahedral geometry around the metal ions, has been supported by magnetic susceptibility measurements.
The results of electron spin resonance & 1H-NMR spectra have supported the results of other spectral techniques. Kinetic and thermodynamic parameters were computed
from the thermal data using Coats and Redfern method, which confirm first order kinetics. Powder diffraction determines the
cell parameters of the complexes. 相似文献
6.
Victor V. Dotsenko Sergey G. Krivokolysko Alexander N. Chernega Victor P. Litvinov 《Monatshefte für Chemie / Chemical Monthly》2007,138(1):35-42
Summary. 3,5,7,11-Tetraazatricyclo[7.3.1.02,7]tridec-2-ene derivatives were prepared in one-pot manner from N-methylmorpholinium 6-amino-3,5-dicyano-4-spiro(1′-cycloalkane)-1,4-dihydropyridine-2-thiolates, primary amines, and formaldehyde
in 70–88% yields. The structure of 5,11-dibenzyl-13-spiro(1′-cyclopentane)-8-thioxo-3,5,7,11-tetraazatricyclo[7.3.1.02,7]tridec-2-ene-1,9-dicarbonitrile was determined by X-ray diffraction analysis. 相似文献
7.
E. Yu. Fursova O. V. Kuznetsova V. I. Ovcharenko G. V. Romanenko A. S. Bogomyakov M. A. Kiskin I. L. Eremenko 《Russian Chemical Bulletin》2007,56(9):1805-1808
A method was developed for the synthesis of mixed-metal heterospin compounds with the direct coordination of the nitroxide
fragment based on the replacement of acetonitrile molecules in the heterotrinuclear complex [Co2Gd(NO3)Piv6(CH3CN)2] with nitroxide molecules. The molecular and crystal structure of the heterospin mixed-ligand heterotrinuclear CoII, GdIII, CoII complex [Co2Gd(NO3)Piv6(NIT-Me)2], where NIT-Me is stable nitronyl nitroxide, was established. The magnetic properties of this complex were investigated in
the temperature range of 2–300 K. The coordination of nitroxide groups to CoII ions is responsible for strong exchange interactions between the unpaired electrons in the exchange clusters {>-·O-CoII}, resulting in the virtually complete spin coupling between each coordinated >N-·O group and one of the unpaired electrons
of each CoII ion at temperatures below 200 K.
Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1742–1745, September, 2007. 相似文献
8.
Hasan Marai Ewa Kita Emilia Kiersikowska Sylwia Kuchta Anna Bajek Tomasz Drewa 《Transition Metal Chemistry》2012,37(4):337-344
Three chromium(III) complexes with asparagine (Asn) and histidine (His) of the [Cr(ox)2(Aa)]2− type, where Aa = N,O–Asn, N,O–His or N,N′–His, were obtained and characterized in solution. The complexes with N,O–Aa undergo acid-catalysed aquation to give a free amino acid and cis-[Cr(ox)2(H2O)2]−, whereas the complex with N,N′–His undergoes parallel reaction paths: (1) isomerization to the N,O–His complex and (2) liberation of an oxalate ligand. Kinetics of the N,O–Aa complexes in HClO4 media were studied spectrophotometrically under pseudo-first-order conditions. The absorbance changes were attributed to
the chelate ring opening at the Cr–N bond. The linear dependence of rate constants on [H+] was established, and a mechanism for the chelate ring cleavage was postulated. The existence of a metastable intermediate
with O-monodentate Aa ligand was proved experimentally. Effect of [Cr(ox)2(Aa)]2− on 3T3 fibroblasts proliferation was studied. The tests revealed low cytotoxicity of the complexes. Complexes with Ala, His
and Cys are good candidates for biochromium sources. 相似文献
9.
A. S. Volk I. N. Krasikova S. D. Anastyuk P. S. Dmitrenok T. F. Solov’eva 《Chemistry of Natural Compounds》2007,43(5):519-524
The structure of lipid A from the marine γ-proteobacterium Pseudoalteromonas nigrifaciens IAM 13010T that was prepared by hydrolysis of the corresponding lipopolysaccharide by acetic acid (1%) was determined by chemical analysis,
13C NMR spectroscopy, and MALDI/TOF and LSIMS mass spectrometry. It was shown that lipid A is a β-1,6-bonded disaccharide of glucosamine that is substituted by two phosphoric acids (in the C1 and C4′ positions), two (R)-3-hydroxyalkanoic
(normal and branched) acids with ester bonding (at the C3 and C3′-positions), and (R)-3-hydroxydodecanoic and (R)-3-dodecanoyloxydodecanoic
acids (both with amide bonding at C2′ and C2, respectively). It was hypothesized that this type of structure is typical of
lipid A from bacteria of the genus Pseudoalteromonas in general.
__________
Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 425–429, September–October, 2007. 相似文献
10.
Zal U’yun Wan Mahmood Che Abd Rahim Mohamed Zaharudin Ahmad Abdul Kadir Ishak Norfaizal Mohamed 《Journal of Radioanalytical and Nuclear Chemistry》2011,289(1):91-95
Protactinium and thorium activities were measured in eight surface sediment taken in 2004 to determine effectiveness scavenging
of 231Pa at Sabah–Sarawak coastal waters. The result found that activity ratios of 231Paex/230Thex were ranged from 0.07 to 0.13 at all sampling stations. The high 231Paex/230Thex activity ratio than the production ratio of 0.093 in seawater at station SR 01, SR 02, SR 04, SB 02 and SB 05, revealed that
231Pa is effectively removed from the water column into the sediment in comparison with 230Th at those stations. Low percentage of 230Thex (90–95%) in comparison with 231Paex at all stations can be attributed to less efficiently scavenged of 230Th onto particles prior deposited at the marine sediment bed. 相似文献
11.
Ya-Guang Chen Fan-Xia Meng Hai-Jun Pang Dong-Mei Shi Yu Sun 《Journal of Cluster Science》2007,18(2):396-405
A novel uranyl complex with dimeric lacunary polyoxoanion like open-mouthed clam, Na5[(A-α-SiW9O33H3)2K{UO2(H2O)}2], was prepared and characterized by elemental analysis, infrared and ultraviolet–visible spectroscopy and single crystal
X-ray diffraction. In the anion, two A-α-SiW9O3410− groups share two terminal oxygen atoms Od′ derived from removal of three corner-shared W atoms from saturated α-Keggin anion, forming a dimeric anion with an open
mouth in which potassium ion and uranyl ions are coordinated. Uranium atom adopts a pentagonal bipyramidal geometry. The coordinating
anions are linked by sodium ions via coordination of terminal or bridging oxygen atoms, forming two-dimensional layer arrangement.
Between the layers are the hydrogen bonds from which a supramolecular architecture is created. UV–VIS spectrum gives W–O and
U–O charge transfer transitions at 230–265 and 432 nm, showing the change of geometry of the polyanion and weakening of the
U–O bonds of the uranyl cation.
Electronic supplementary material The online version of this article () contains supplementary material, which is available to authorized users. 相似文献
12.
V. L. Lobachev G. P. Zimtseva E. S. Rudakov 《Theoretical and Experimental Chemistry》2005,41(5):302-309
It was found that nitrite anions are effective activators of hydrogen peroxide in the reaction with diethyl sulfide. The observed
kinetics are consistent with the proposed intermediate formation of peroxynitrous acid (ONOOH). The rate constants for the
reaction of diethyl sulfide Et2S with the acid ONOOH (k0 = 1.8⋅103 L/mol⋅s) and with the anion ONOO− (k− = 6⋅10−2 L/mol⋅s) are respectively 105 and three times higher than with hydrogen peroxide.
__________
Translated from Teoreticheskaya i Eksperimental'naya Khimiya, Vol. 41, No. 5, pp. 290–295, September–October, 2005. 相似文献
13.
H. N. Altshuler L. P. Abramova N. V. Malyshenko G. Yu. Shkurenko E. V. Ostapova 《Russian Chemical Bulletin》2005,54(8):1978-1981
The ion-exchange equilibrium in network polymers obtained from cis-2,8,14,20-tetraphenyl-4,6,10,12,16,18,22,24-octahydroxycalix[4]arene by template synthesis on cations Na+, K+, and Ba2+ as matrices was studied. The selectivity coefficients of ion exchanges Ba2+-H+, Na+-H+, K+-H+, Na+-K+, and Na+-NH4
+ were determined. The template synthesis enhanced the affinity of the polymers to matrix-forming cations by 6–8 kJ mol−1.
__________
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1919–1922, August, 2005. 相似文献
14.
Liqin Liu Min Zhang Guangrong Zhong Xuebin Wang 《Journal of Radioanalytical and Nuclear Chemistry》2011,287(3):847-852
A conjugate of 6-hydrazinopyridine-3-carboxylic acid (HYNIC) with the amino analogue of metronidazole (MN) was synthesized
through a multiple-step reaction. HYNIC-MN could be labeled easily and efficiently with 99mTc using N-(2-hydroxy-1,1-bis(hydroxymethyl)ethyl)glycine (tricine) and ethylenediamine -N,N′-diacetic acid (EDDA) as coligands to form the 99mTc–HYNIC–MN complex in high yield (>95%). Its partition coefficient indicated that it was a good hydrophilic complex. The
tumor cell experiment showed that the 99mTc–HYNIC–MN complex had a certain hypoxic selectivity. The biodistribution studies of 99mTc–HYNIC–MN in Kunming mice bearing S180 tumor showed a favorable tissue distribution profile with high tumor uptake, and
low or negligible accumulation in non-target organs, suggesting 99mTc–HYNIC–MN would be a novel potential tumor hypoxia imaging agent. 相似文献
15.
Bin Peng Hui Chao Bin Sun Feng Gao Liang-Nian Ji Jian Zhang 《Transition Metal Chemistry》2007,32(2):271-277
Two novel cobalt(III) mixed-polypyridyl complexes
[Co(bpy)2(dpta)]3+ and [Co(bpy)2(amtp)]3+ (bpy = 2,2′-bipyridine, dpta = dipyrido-[3,2-a;2′,3′-c]-thien-[3,4-c]azine, amtp = 3-amino-1,2,4-triazino[5,6-f]-1,10-phenanthroline)
have been synthesized and characterized. The interaction of CoIII complexes with calf thymus DNA was investigated by spectroscopic and viscosity measurements. Results suggest that the two
complexes bind to DNA via an intercalative mode. Moreover, CoIII complexes have been found to promote the photocleavage of plasmid DNA pBR322 under irradiation at 365 nm. The mechanism studies
reveal that hydroxyl radical (OH•) is likely to be the reactive species responsible for the cleavage of plasmid DNA by [Co(bpy)2(dpta)]3+ and superoxide anion radical (O
2
•−
) acts as the key role in the cleavage reaction of plasmid DNA by [Co(bpy)2(amtp)]3+. 相似文献
16.
D. A. Loginov M. M. Vinogradov Z. A. Starikova P. V. Petrovskii A. R. Kudinov 《Russian Chemical Bulletin》2007,56(11):2162-2165
The visible light irradiation of the [(η5-C6H7)Fe(η-C6H6)]+ cation (1) in acetonitrile resulted in the substitution of the benzene ligand to form the labile acetonitrile species [(η5-C6H7)Fe(MeCN)3]+ (2). The reaction of 1 with ButNC in MeCN produced the stable isonitrile complex [(η5-C6H7)Fe(ButNC)3]+ (3). The photochemical reaction of cation 1 with pentaphosphaferrocene Cp*Fe(η-cyclo-P5) afforded the triple-decker cation with the bridging pentaphospholyl ligand, [(η5-C6H7)Fe(μ-η:η-cyclo-P5)FeCp*]+ (4). The latter complex was also synthesized by the reaction of cation 2 with Cp*Fe(η-cyclo-P5). The structure of the complex [3]PF6 was established by X-ray diffraction.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2088–2091, November, 2007. 相似文献
17.
The ortho-metalated complex [Pd(x){κ
2
(C,N)-[C6H4CH2NRR′ (Y)}] (2a–4a and 2b–3b) was prepared by refluxing in benzene equimolecular amounts of Pd(OAc)2 and secondary benzylamine [a, EtNHCH2Ph; b, t-BuNHCH2Ph followed by addition of excess NaCl. The reaction of the complexes [Pd(x){κ
2
(C,N)-[C6H4CH2NRR′ (Y)}] (2a–4a and 2b–3b) with a stoichiometric amount of Ph3P=C(H)COC6H4-4-Z (Z = Br, Ph) (ZBPPY) (1:1 molar ratio), in THF at low temperature, gives the cationic derivatives [Pd(OC(Z-4-C6H4C=CHPPh3){κ
2
(C,N)-[C6H4CH2NRR′(Y)}] (5a–9a, 4b–6b, and 4b′–6b′), in which the ylide ligand is O-coordinated to the Pd(II) center and trans to the ortho-metalated C(6)H(4) group, in an “end-on
carbonyl”. Ortho-metallation, ylide O-coordination, and C-coordination in complexes (5a–9a, 4b–6b, and 4b′–6b′) were characterized by elemental analysis as well as various spectroscopic techniques. 相似文献
18.
V. V. Dotsenko S. G. Krivokolysko V. P. Litvinov 《Chemistry of Heterocyclic Compounds》2007,43(11):1455-1459
5,11-Disubstituted derivatives of 1′-isopropyl-8-thioxospiro[3,5,7,11-tetrazatricyclo[7.3.1.02,7]tridec-2-ene-13,4′-piperidine]-1,9-dicar bonitrile was obtained by the interaction of 10-amino-9-aza-3-azonia-7,11-dicyano-3-isopropylspiro[5,5]undeca-7,10-diene-8-thiolate
with 2 equiv. of a primary amine and excess of formaldehyde. An anomalous reaction product was obtained with o-toluidine — 7,9-dicyano-1′-isopropyl-3-(2-methylphenyl)-1,2,3,4-tetrahydrospiro[pyrido[1,2-a][1,3,5]triazine-8,4′-piper idinium]-6-thiolate.
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Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, 1709–1713, November, 2007. 相似文献
19.
Zal U’yun Wan Mahmood Che Abd Rahim Mohamed Mei Wo Yii Zaharudin Ahmad Kamaruzzaman Ishak Abdul Kadir Ishak 《Journal of Radioanalytical and Nuclear Chemistry》2010,286(1):107-113
Inventories and fluxes of 210Pb, 228Ra and 226Ra were determined in sediment cores collected at nine stations covering of the southern South China Sea and Malacca Straits
with the thickness of water column between 42 and 83 m depth. The inventories of 210Pb, 228Ra and 226Ra were calculated range from 0.15–2.55 Bq cm−2, 0.05–0.40 Bq cm−2 and 6.83–83.63 Bq cm−2, meanwhile the fluxes ranged from 0.005–0.079 Bq cm−2 yr−1, 0.009–0.048 Bq cm−2 yr−1 and 0.003–0.037 Bq cm−2 yr−1, respectively. The results show that the highest inventories and fluxes for 210Pb, 228Ra and 226Ra were found at station WC 01 and EC 05. Because there are additional sources of 210Pb, 228Ra and 226Ra, where water transport will brings more dissolved isotopes, influence of the transportation and deposition of suspended
particles, fast rate of regeneration and greater production of those radionuclides and others. 相似文献
20.
D. K. Das P. N. Pathak S. Kumar V. K. Manchanda 《Journal of Radioanalytical and Nuclear Chemistry》2009,281(3):449-455
Sorption behavior of 241Am (~10−9 M) on naturally occurring mineral pyrite (particle size: ≤70 μm) has been studied under varying conditions of pH (2–11),
and ionic strength (0.01–1.0 M (NaClO4)). The effects of humic acid (2 mg/L), other complexing anions (1 × 10−4 M CO3
2−, SO4
2−, C2O4
2− and PO4
3−), di- and trivalent metal ions (1 × 10−3 M Mg2+, Ca2+ and Nd3+) on sorption behavior of Am3+ at a fixed ionic strength (I = 0.10 M (NaClO4)) have been studied. The sorption of 241Am on pyrite increased with pH from 2.8 (84%) to 8.1 (97%). The sorption of 241Am decreased with ionic strength at low pH values (2 ≤ pH ≤ 4), but was insensitive in the pH range of 4–10, suggesting the
formation of outer-sphere complexes on pyrite surface at lower pH, and inner-sphere complexes at higher pH values. The sorption
of 241Am increased in the presence of (i) humic acid (5 < pH < 7.5), and (ii) C2O4
2− (2 < pH < 3). By contrast, other complexing anions such as (carbonate, phosphate, and sulphate) showed negligible influence
on 241Am sorption. The presence of Mg2+, Ca2+ ions showed marginal effect on the sorption profile of 241Am; while the presence of Nd3+ ion suppressed its sorption significantly under the conditions of present study. The sorption of 241Am on pyrite decreased with increased temperature indicating an exothermic process. 相似文献