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1.
Speciation analysis of orthophosphate and myo‐inositol hexakisphosphate in soil‐ and plant‐related samples by high‐performance ion chromatography combined with inductively coupled plasma mass spectrometry 下载免费PDF全文
Ariana Rugova Markus Puschenreiter Jakob Santner Lisa Fischer Stefan Neubauer Gunda Koellensperger Stephan Hann 《Journal of separation science》2014,37(14):1711-1719
A novel method based on high‐performance ion chromatography inductively coupled plasma mass spectrometry employing strong anion exchange chromatography with HNO3 gradient elution for simultaneous analysis of orthophosphate and myo‐inositol hexakisphosphate (IP6) in soil solution and plant extracts is presented. As inductively coupled plasma mass spectrometry analysis of phosphorus at m/z 31 is hampered by N‐based interferences, 31P was measured as 31P16O+ at m/z 47 employing dynamic reaction cell technique with O2 as reaction gas. Orthophosphate and IP6 were separated within a total chromatographic run‐time of 12 min revealing a limit of detection of 0.3 μmol/L. The coefficients of determination obtained in a working range of 1–100 and 1–30 μmol/L were 0.9991 for orthophosphate and 0.9968 for IP6, respectively. The method was successfully applied to extracts from three different soils as well as root and shoot extracts of Brassica napus L. The precision of three independently prepared soil extracts was in the range of 4–10% relative standard deviation for PO43? and 3–8% relative standard deviation for IP6. Soil adsorption/desorption kinetics for IP6/orthophosphate were performed for investigating the sorption behavior of the two P species in the experimental soils. 相似文献
2.
Metal(II) Ion Complexes with 5‐(Pyrazin‐2‐yl)‐2,4‐dihydro‐3H‐1,2,4‐triazole‐3‐thione; Synthesis,Structural Characterization,Acid‐base,and Complexing Properties in Solution 下载免费PDF全文
Aleksander Kufelnicki Jolanta Jaciubek‐Rosińska Marta Sobiesiak Agata Paneth Julia Jezierska Elzbieta Budzisz 《无机化学与普通化学杂志》2017,643(16):1067-1074
The study reports the synthesis of complexes Co(HL)Cl2 ( 1 ), Ni(HL)Cl2 ( 2 ), Cu(HL)Cl2 ( 3 ), and Zn(HL)3Cl2 ( 4 ) with the title ligand, 5‐(pyrazin‐2‐yl)‐1,2,4‐triazole‐5‐thione (HL), and their characterization by elemental analyses, ESI‐MS (m/z), FT‐IR and UV/Vis spectroscopy, as well as EPR in the case of the CuII complex. The comparative analysis of IR spectra of the metal ion complexes with HL and HL alone indicated that the metal ions in 1 , 2 , and 3 are chelated by two nitrogen atoms, N(4) of pyrazine and N(5) of triazole in the thiol tautomeric form, whereas the ZnII ion in 4 is coordinated by the non‐protonated N(2) nitrogen atom of triazole in the thione form. pH potentiometry and UV/Vis spectroscopy were used to examine CoII, NiII, and ZnII complexes in 10/90 (v/v) DMSO/water solution, whereas the CuII complex was examined in 40/60 (v/v) DMSO/water solution. Monodeprotonation of the thione triazole in solution enables the formation of the L:M = 1:1 species with CoII, NiII and ZnII, the 2:1 species with CoII and ZnII, and the 3:1 species with ZnII. A distorted tetrahedral arrangement of the CuII complex was suggested on the basis of EPR and Vis/NIR spectra. 相似文献
3.
Functionalized poly‐N,N‐dimethylaniline film was prepared by adsorption of ferrocyanide onto the polymer forming at the surface of carbon paste electrode (CPE) in aqueous solution by using potentiostatic method. The electrocatalytic ability of poly‐N,N‐dimethylaniline/ferrocyanide film modified carbon paste electrode (PDMA/FMCPE) was demonstrated by oxidation of cysteamine. Cyclic voltammetry and chronoamperometry techniques were used to investigate this ability. Results showed that pH 7.00 is the most suitable for this purpose. It is found that the catalytic reaction rate constant, (kh), is equal to 2.142×103 M?1 s?1 by the data of chronoamperometry. The catalytic reduction peak current was linearly dependent on the cysteamine concentration and the linearity range obtained was 8.00×10?5 M–1.14×10?2 M. Detection limit was determined 7.97×10?5 M (2σ). This method has been successfully employed for quantification of cysteamine in real sample. 相似文献
4.
Sainan Zhang Zhengcai Ju Huida Guan Lu Yu Zhengtao Wang Yuqing Zhao 《Biomedical chromatography : BMC》2019,33(11)
Notoginsenoside R1 (NGR1), a diagnostic protopanaxatriol‐type (ppt‐type) saponin in Panax notoginseng, possesses potent biological activities including antithrombotic, anti‐inflammatory, neuron protection and improvement of microcirculation, yet its pharmacokinetics and metabolic characterization as an individual compound remain unclear. The aim of this study was to investigate the exposure profile of NGR1 in rats after oral and intravenous administration and to explore the metabolic characterization of NGR1. A simple and sensitive ultra‐fast liquid chromatographic–tandem mass spectrometric method was developed and validated for the quantitative determination of NGR1 and its major metabolites, and for characterization of its metabolic profile in rat plasma. The blood samples were precipitated with methanol, quantified in a negative multiple reaction monitoring mode and analyzed within 6.0 min. Validation parameters (linearity, precision and accuracy, recovery and matrix effect, stability) were within acceptable ranges. After oral administration, NGR1 exhibited dose‐independent exposure behaviors with t1/2 over 8.0 h and oral bioavailability of 0.25–0.29%. A total of seven metabolites were characterized, including two pairs of epimers, 20(R)‐notoginsenoside R2/20(S)‐notoginsenoside R2 and 20(R)‐ginsenoside Rh1/20(S)‐ginsenoside Rh1, with the 20(R) form of saponins identified for the first time in rat plasma. Five deglycometabolites were quantitatively determined, among which 20(S)‐notoginsenoside R2, ginsenoside Rg1, ginsenoside F1 and protopanaxatriol displayed relatively high exploration, which may partly explain the pharmacodynamic diversity of ginsenosides after oral dose. 相似文献
5.
Stefan Spirk Dr. Ferdinand Belaj Prof. Dr. Martin Nieger Dr. Harald Köfeler Dr. Gerald N. Rechberger Dr. Rudolf Pietschnig Univ.‐Doz. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(37):9521-9529
The synthesis of a series of m‐terphenyl‐substituted tetrafluorosilicates with different cations (Na+, K+, Rb+, Cs+, Ag+, Tl+) is described and the interactions between the anion and cation are investigated in the solid, solution, and gas states by using multinuclear NMR spectroscopy, X‐ray diffraction, and ion cyclotron resonance Fourier‐transform mass spectrometry (ICR‐FT‐MS). In solution, heteronuclear NMR spectroscopy parameters show only limited sensitivity to the nature of the cation, which furthermore can be affected by solvent effects. More pronounced effects are observed in the structural data obtained from X‐ray diffraction studies, which are in good agreement with experimental gas‐phase data from ESIMS. ESIMS also reveals the existence of dimeric species of the type [M(DmpSiF4)2]? (Dmp=2,6‐dimesitylphenyl), the stability of which was determined by normalized collision energy experiments. 相似文献
6.
Christine Kunze Ion Neda Matthias Freytag Peter G. Jones Reinhard Schmutzler 《无机化学与普通化学杂志》2002,628(3):545-552
The reaction behaviour of 1, 3, 5‐triaza‐2σ3λ3‐phosphorin‐4, 6‐dionyloxy‐substituted calix[4]arenes towards mono‐ and binuclear rhodium and platinum complexes was investigated. Special attention was directed to structure and dynamic behaviour of the products in solution and in the solid state. Depending on the molar ratio of the reactands, the reaction of the tetrakis(triazaphosphorindionyloxy)‐substituted calix[4]arene ( 4 ) and its tert‐butyl‐derivative ( 1 ) with [(cod)RhCl]2 yielded the mono‐ and disubstituted binuclear rhodium complexes 2 , 3 , and 5 . In all cases, a C2‐symmetrical structure was proved in solution, apparently caused by a fast intramolecular exchange process between cone conformation and 1, 3‐alternating conformation. The X‐ray crystal structure determination of 5 confirmed [(calixarene)RhCl]2‐coordination through two opposite phosphorus atoms with a P ⃜P separation of 345 pm. The complex displays crystallographic inversion symmetry, and the Rh2Cl2 core is thus exactly planar. Reaction of 1 and of the bis(triazaphosphorindionyloxy)‐bis(methoxy)‐substituted tert‐butyl‐calix‐[4]arene ( 7 ) with (cod)Rh(acac) in equimolar ratio and subsequent reaction with HBF4 led to the expected cationic monorhodium complexes 5 and 8 , involving 1, 3‐alternating P‐Rh‐P‐coordination. The cone conformation in solution was proved by NMR spectroscopy and characteristic values of the 1J(PRh) coupling constants in the 31P‐NMR‐spectra. Reaction of equimolar amounts of 4 with (cod)Rh(acac) or (nbd)Rh(acac) led, by substitution of the labile coordinated acetylacetonato and after addition of HBF4, to the corresponding mononuclear cationic complexes 9 and 10 . Only two of the four phosphorus atoms in 9 and 10 are coordinated to the central metal atom. Displacement of either cycloocta‐1, 5‐diene or norbornadiene was not observed. For both compounds, the cone conformation was proved by NMR spectroscopy. Reaction of 4 with (cod)PtCl2 led to the PtCl2‐complex ( 11 ). As for all compounds mentioned above, only two phosphorus atoms of the ligand coordinate to platinum, while two phosphorus atoms remain uncoordinated (proved by δ31P and characteristic values of 1J(PPt)). NMR‐spectroscopic evidence was found for the existence of the cone conformation in the cis‐configuration of 11 . 相似文献
7.
The competitive removal of Pb2+, Cu2+, and Cd2+ ions from aqueous solutions by the copolymer of 2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid (AMPS) and itaconic acid (IA), P(AMPS‐co‐IA), was investigated. Homopolymer of AMPS (PAMPS) was also used to remove these ions from their aqueous solution. In the preparation of AMPS–IA copolymer, the molar percentages of AMPS and IA were 80 and 20, respectively. In order to observe the changes in the structures of polymers due to metal adsorption, FTIR spectra by attenuated total reflectancetechnique and scanning electron microscopy (SEM) pictures of the polymers were taken both before and after adsorption experiments. Total metal ion removal capacities of PAMPS and P(AMPS‐co‐IA) were 1.685 and 1.722 mmol Me2+/gpolymer, respectively. Experimental data were evaluated to determine the kinetic characteristics of the adsorption process. Competitive adsorption of Pb2+, Cu2+, and Cd2+ ions onto both PAMPS and P(AMPS‐co‐IA) was found to fit pseudo‐second‐order type kinetics. In addition, the removal orders in the competitive adsorption of these metal ions onto PAMPS and P(AMPS‐co‐IA) were found to be Cd2+ > Pb2+ > Cu2+ and Pb2+ > Cd2+ > Cu2+, respectively. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
8.
2‐Nitroimino‐5‐nitro‐hexahydro‐1,3,5‐triazine (NNHT), was synthesized and its structure was determined by single‐crystal X‐ray diffraction. The crystal is monoclinic, space group P21/c with crystal parameters of a = 9.4031(13) Å, b = 8.5891(12) Å, c = 9.0200(13) Å, β = 91.213(2)°, V = 728.33(18) Å3, Z = 4, F(000) = 392, Dc = 1.734 g/cm3. The experimental geometry of NNHT was input to Gaussian‐03W program and optimized using DFT‐B3LYP/6‐311++G** method. The IR frequencies and NMR chemical shift were carried out and compared well with those of the experimental. The atomic net charges and the population analysis are discussed. The heat of formation (HOF) for NNHT was evaluated by designing an isodesmic reaction. The detonation velocity (D) and detonation pressure (P) were estimated by using the well known Kamlet‐Jacobs equation, based on the theoretical HOF. 相似文献
9.
Kerli Martin Sandip A. Kadam Ulriika Mattinen Johan Bobacka Ivo Leito 《Electroanalysis》2019,31(6):1061-1066
The construction and study of solid‐contact acetate‐selective electrodes is described using a 1,3‐bis(carbazolyl)urea derivative as a neutral hydrogen‐bonding ionophore and poly(3,4‐ethylenedioxythiophene) as the solid contact. It was shown recently that this ionophore binds acetate (logKass=4.98) that is used as primary ion in this study. The electrodes show linearity over the activity range of 10?4.50–10?1.10 with a sub‐Nernstian slope of ?51.3 mV per decade and a detection limit of 10?5.00. The anion‐selectivity pattern of these electrodes deviates markedly from the Hofmeister pattern. When adding ionophore to the membrane the logarithm of the selectivity coefficient (logK) for SCN? decreased from 6.5 to 1.2, logK for I? decreased from 5.7 to 0.9, logK for NO3? decreased from 4.3 to 0.6 and logK for Br? decreased from 3.3 to 0.1. The selectivity coefficients of hydrophilic anions such as Cl?, F?, HPO42?, and SO42? are significantly lower than in case of the ionophore‐free membrane. It was discovered that the constructed electrodes are also relatively selective to bicarbonate. This work is an important step towards the further development of solid‐contact anion‐selective electrodes. 相似文献
10.
Seong Huh Young Jun Park Alan. J. Lough Moo‐Jin Jun 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(4):416-417
The title compound, [RuH(C6H8BN4)(C21H21P)2(CO)], possesses two trans‐disposed tri‐p‐tolylphosphines in axial positions and the remaining ligands in equatorial positions. The overall geometry of the RuII ion is a distorted octahedral structure. The P—Ru—P axis deviates from linearity by about 13°. This distortion arises mainly from the steric congestion between the bulky phosphine moieties and the tetrahedral dihydrobis(pyrazol‐1‐yl)borate ligands. 相似文献
11.
Time‐Resolved Assembly of Cluster‐in‐Cluster {Ag12}‐in‐{W76} Polyoxometalates under Supramolecular Control 下载免费PDF全文
Caihong Zhan Jamie M. Cameron Jing Gao Jamie W. Purcell De‐Liang Long Leroy Cronin 《Angewandte Chemie (International ed. in English)》2014,53(39):10362-10366
We report the time‐resolved supramolecular assembly of a series of nanoscale polyoxometalate clusters (from the same one‐pot reaction) of the form: [H(10+m)Ag18Cl(Te3W38O134)2]n, where n=1 and m=0 for compound 1 (after 4 days), n=2 and m=3 for compound 2 (after 10 days), and n=∞ and m=5 for compound 3 (after 14 days). The reaction is based upon the self‐organization of two {Te3W38} units around a single chloride template and the formation of a {Ag12} cluster, giving a {Ag12}‐in‐{W76} cluster‐in‐cluster in compound 1 , which further aggregates to cluster compounds 2 and 3 by supramolecular Ag‐POM interactions. The proposed mechanism for the formation of the clusters has been studied by ESI‐MS. Further, control experiments demonstrate the crucial role that TeO32?, Cl?, and Ag+ play in the self‐assembly of compounds 1 – 3 . 相似文献
12.
Alleno‐Acetylenic Cage (AAC) Receptors: Chiroptical Switching and Enantioselective Complexation of trans‐1,2‐Dimethylcyclohexane in a Diaxial Conformation 下载免费PDF全文
Cornelius Gropp Dr. Nils Trapp Prof. Dr. François Diederich 《Angewandte Chemie (International ed. in English)》2016,55(46):14444-14449
Four enantiopure 1,3‐diethynylallenes (DEAs) with OH termini were attached to the rim of a resorcin[4]arene cavitand. The system undergoes conformational switching between a cage form, closed by a circular H‐bonding array, and an open form, with the tertiary alcohol groups reaching outwards. The cage form is predominant in apolar solvents, and the open conformation in small, polar solvents. Both states were confirmed in solution and in X‐ray co‐crystal structures. ECD spectra of the alleno‐acetylenic cages (AACs) are highly conformation sensitive, the longest wavelength Cotton effect at 304 nm switches from Δ?=+191 m ?1 cm?1 for open (P)4‐AAC?acetonitrile to Δ?=?691 m ?1 cm?1 (ΔΔ?=882 m ?1 cm?1) for closed (P)4‐AAC?cyclohexane. Complete chiral resolution of (±)‐trans‐1,2‐dimethylcyclohexane was found in the X‐ray structures, with (P)4‐AAC exclusively bound to the (R,R)‐ and (M)4‐AAC to the (S,S)‐guest. Guest inclusion occurs in a higher energy diaxial conformation. 相似文献
13.
Dr. Yosuke Demizu Prof. Mitsunobu Doi Dr. Masaaki Kurihara Prof. Tokumi Maruyama Prof. Hiroshi Suemune Prof. Masakazu Tanaka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(8):2430-2439
Chiral cyclic α,α‐disubstituted amino acids, (3S,4S)‐ and (3R,4R)‐1‐amino‐3,4‐(dialkoxy)cyclopentanecarboxylic acids ((S,S)‐ and (R,R)‐Ac5cdOR; R: methyl, methoxymethyl), were synthesized from dimethyl L ‐(+)‐ or D ‐(?)‐tartrate, and their homochiral homoligomers were prepared by solution‐phase methods. The preferred secondary structure of the (S,S)‐Ac5cdOMe hexapeptide was a left‐handed (M) 310 helix, whereas those of the (S,S)‐Ac5cdOMe octa‐ and decapeptides were left‐handed (M) α helices, both in solution and in the crystal state. The octa‐ and decapeptides can be well dissolved in pure water and are more α helical in water than in 2,2,2‐trifluoroethanol solution. The left‐handed (M) helices of the (S,S)‐Ac5cdOMe homochiral homopeptides were exclusively controlled by the side‐chain chiral centers, because the cyclic amino acid (S,S)‐Ac5cdOMe does not have an α‐carbon chiral center but has side‐chain γ‐carbon chiral centers. 相似文献
14.
Bhaskar R. Aluri Dr. Sebastian Burck Dr. Dietrich Gudat Prof. Dr. Mark Niemeyer Dr. Oldamur Holloczki Laszlo Nyulaszi Prof. Dr. Peter G. Jones Prof. Dr. Joachim Heinicke Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(45):12263-12272
Synthetic and structural aspects of the phosphanylation of 1,3‐benzazaphospholides 1Li , ambident benzofused azaphosphacyclopentadienides, are presented. The unusual properties of phospholyl‐1,3,2‐diazaphospholes inspired us to study the coupling of 1Li with chlorodiazaphospholene 2 , which led to the N‐substituted product 3 . Reaction of 1Li with chlorodiphenyl‐ and chlorodicyclohexylphosphane likewise gave N‐phosphanylbenzazaphospholes 4 and 5 , whereas with the more bulky di‐tert‐butyl‐ and di‐1‐adamantylchlorophosphanes, the diphosphanes 6 and 7 are obtained; in the case of 7 they are isolated as a dimeric LiCl(THF) adduct. Structural information was provided by single‐crystal X‐ray diffraction and solution NMR spectroscopy experiments. 2D exchange spectroscopy confirmed the existence of two rotamers of the aminophosphane 5 at room temperature; variable‐temperature NMR spectroscopy studies of 6 revealed two dynamic processes, low‐temperature inversion at ring phosphorus (ΔH≠=22 kJ mol?1, ΔS≠=2 J K?1 mol?1) and very low‐temperature rotation of the tBu2P group. Quantum chemical studies give evidence that 2‐unsubstituted benzazaphospholides prefer N‐phosphanylation, even with bulky chlorophosphanes, and that substituents at the 2‐position of the heterocycle are crucial for the occurrence of P–N rotamers and for switching to alternative P‐substitution, beyond a threshold steric bulk, by both P‐ and 2‐position substituents. 相似文献
15.
Surface Nanostructures Composed of Thiolated Cyclodextrin/Au and Fe Species: Gas‐ and Liquid‐Phase Preparation 下载免费PDF全文
Sona Halaszova Dr. Monika Jerigova Dr. Dusan Lorenc Michal Prochazka Prof. Dr. Dusan Velic 《Chemphyschem》2016,17(15):2295-2299
Supramolecular surface nanostructures have application potential as functional devices. The complex combination of thiolated cyclodextrin, chemisorbed on an Au surface (Au‐S‐CD), with deposited Fe species is studied by secondary ion mass spectrometry. The Fe species are prepared by pulsed laser ablation in water and thermal effusion in vacuum. Using laser ablation in water, the solution of Fe species is dropped on Au‐S‐CD, where mass peaks at 1227 m/z, 1243 m/z, and 1260 m/z are observed and assigned to C42H68O34SNa‐Fe+, C42H68O34SK‐Fe+ together with C42H68O34SNa‐FeO+, and C42H68O34SK‐FeO+, respectively. On the other hand, laser ablation directly linked to the Au‐S‐CD surface results in desorption of CD‐S. Thermal effusion, even with a cooled surface, was negative with respect to the complex observation. Laser ablation results in the formation of a supramolecular host–guest complex of the form Au‐S‐CD‐Fe, and in the formation of an adduct of the form Au‐S‐CD‐FeO. 相似文献
16.
Tatyana Saplinova Vadym Bakumov Tobias Gmeiner Jörg Wagler Marcus Schwarz Edwin Kroke Prof. Dr. 《无机化学与普通化学杂志》2009,635(15):2480-2487
The title compound C6N7(NHNH2)3 ( 1 ) was obtained from melem C6N7(NH2)3 or melon [C6N7(NH2)NH]n and hydrazine by an autoclave synthesis. Upon treatment with a 10 % HCl solution it is transformed into the trihydrochloride [C6N7(NHNH3)3]Cl3 ( 2 ). Compounds 1 and 2 were analysed with 13C NMR, 15N NMR, FTIR and Raman spectroscopy. Furthermore, the single‐crystal X‐ray structure of the pentahydrate of 2 is reported (P\bar{1} , a = 674.96(3), b = 1214.17(6), c = 1272.15(6) pm, α = 66.288(2)°, β = 75.153(2)°, γ = 80.420(2)°, V = 920.30(8)·106 pm3, Z = 2, T = 90(2) K). The thermal decomposition of 1 and 2 was investigated with TG/DTA. Reaction of 1 with NaNO2/HCl yields triazido‐s‐heptazine, C6N7(N3)3 ( 3 ). Tris(tri‐n‐butylphosphinimino)‐s‐heptazine ( 4 ) was synthesised from 3 and characterised by means of 13C, 31P, 1H NMR, FTIR and MALDI‐TOF spectroscopy. Similar to s‐heptazine derivative 3 , compounds 1 and 4 are precursors for graphitic carbon nitrides, which have attracted considerable attention recently, and to various potential applications, such as flame retardants and (photo) catalysis. 相似文献
17.
Gisbert Großmann Gisela Ohms Kerstin Krüger Konstantin Karaghiosoff Klaus Eckstein Josef Hahn Andreas Hopp Olga L. Malkina Peter Hrobarik 《无机化学与普通化学杂志》2001,627(6):1269-1278
Diselenadiphosphetane Diselenides and Triselenadiphospholane Diselenides – Synthesis and Characterization by 31P and 77Se Solid‐State NMR Spectroscopy 1,3‐Diselena‐2,4‐diphosphetane‐2,4‐diselenides (RPSe2)2 with R = Me, Et, t‐Bu, Ph, 4‐Me2NC6H4, 4‐MeOC6H4 have been synthesized by different methods. The insoluble compounds were investigated by 31P and 77Se solid‐state NMR and the purity of the compounds has been checked by their CP MAS sideband NMR spectra. The structure of the investigated compounds has been confirmed by the isotropic and anisotropic values of the chemical shifts and the 1JP–Se coupling constants. In addition, two new 1,2,4‐triselena‐3,5‐diphospholane‐3,5‐diselenides, (RPSe2)2Se (R = Me, Et), formed under similar synthesis conditions, were investigated. Their structure was derived from the 77Se satellites of 31P solution spectra and from solid‐state spectra. For (t‐BuPSe2)2 the experimentally obtained principal values of phosphorus and selenium shielding tensors are compared with values from IGLO calculations (HF und SOS DFPT). The calculated orientations of the principal axes are discussed. 相似文献
18.
Prof. Tarlok S. Lobana Parminderjit Kaur Amanpreet Kaur Ray J. Butcher 《无机化学与普通化学杂志》2012,638(1):195-200
Ruthenium(II) Complexes containing pyrimidine‐2‐thiolate (pymS–) and bis(diphenylphosphanyl)alkanes [Ph2P–(CH2)m–PPh2, m = 1, dppm; m = 2, dppe; m = 3, dppp; m = 4, dppb] are described. Reactions of [RuCl2L2] (L = dppm, dppp) and [Ru2Cl4L3] (L = dppb) with pyrimidine‐2‐thione (pymSH) in 1:2 molar ratio in dry benzene in the presence of Et3N base yielded the [Ru(pymS)2L] complexes (pymS– = pyrimidine‐2‐thiolate; L = dppm ( 1 ); dppp ( 3 ); dppb ( 4 )). The complex [Ru(pymS)2(dppe)] ( 2 ) was indirectly prepared by the reaction of [Ru(pymS)2(PPh3)2] with dppe. These complexes were characterized using analytical data, IR, 1H, 13C, 31P NMR spectroscopy, and X‐ray crystallography (complex 3 ). The crystal structure of the analogous complex [Ru(pyS)2(dppm)] ( 5 ) with the ligand pyridine‐2‐thiolate (pyS–) was also described. X‐ray crystallographic investigation of complex 3 has shown two four‐membered chelate rings (N, S donors) and one six‐membered ring (P, P donors) around the metal atom. Compound 5 provides the first example in which RuII has three four‐membered chelate rings: two made up by N, S donor ligands and one made up by P, P donor ligand. The arrangement around the metal atoms in each complex is distorted octahedral with cis:cis:trans:P, P:N, N:S, S dispositions of the donor atoms. The 31P NMR spectroscopic data revealed that the complexes are static in solution, except 2 , which showed the presence of more than one species. 相似文献
19.
Quantitative determination of amphetamine in plasma by the use of a novel electrophoric derivatization reagent, o‐(pentafluorobenzyloxycarbonyl)‐2,3,4,5‐tetrafluorobenzoyl chloride is described. Amphetamine can be quantitatively measured down to 49 pg/mL plasma using only 250 μL of sample due to the extraordinary sensitivity of the derivatives under negative ion chemical ionization MS. Plasma samples were made alkaline with carbonate buffer and treated with n‐hexane and reagent solution for 20 min, which, after concentration was measured by negative ion chemical ionization GC‐MS. The method is rapid as extraction and derivatization occur in one single step. [2H5]‐Amphetamine was used as an internal standard. Validation data are given to demonstrate the usefulness of the assay, including specificity, linearity, accuracy and precision, benchtop stability, freeze–thaw stability, autosampler stability, aliquot analysis, and prospective analytical batch size accuracy. 相似文献
20.
Dr. Shenglai Yao Dr. Yun Xiong Dr. Tibor Szilvási Prof. Dr. Hansjörg Grützmacher Prof. Dr. Matthias Driess 《Angewandte Chemie (International ed. in English)》2016,55(15):4781-4785
The first 4π‐electron resonance‐stabilized 1,3‐digerma‐2,4‐diphosphacyclobutadiene [LH2Ge2P2] 4 (LH=CH[CHNDipp]2 Dipp=2,6‐iPr2C6H3) with four‐coordinate germanium supported by a β‐diketiminate ligand and two‐coordinate phosphorus atoms has been synthesized from the unprecedented phosphaketenyl‐functionalized N‐heterocyclic germylene [LHGe‐P=C=O] 2 a prepared by salt‐metathesis reaction of sodium phosphaethynolate (P≡C?ONa) with the corresponding chlorogermylene [LHGeCl] 1 a . Under UV/Vis light irradiation at ambient temperature, release of CO from the P=C=O group of 2 a leads to the elusive germanium–phosphorus triply bonded species [LHGe≡P] 3 a , which dimerizes spontaneously to yield black crystals of 4 as isolable product in 67 % yield. Notably, release of CO from the bulkier substituted [LtBuGe‐P=C=O] 2 b (LtBu=CH[C(tBu)N‐Dipp]2) furnishes, under concomitant extrusion of the diimine [Dipp‐NC(tBu)]2, the bis‐N,P‐heterocyclic germylene [DippNC(tBu)C(H)PGe]2 5 . 相似文献