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91.
Sellmann D Hille A Rösler A Heinemann FW Moll M Brehm G Schneider S Reiher M Hess BA Bauer W 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(4):819-830
In the quest for low-molecular-weight metal sulfur complexes that bind nitrogenase-relevant small molecules and can serve as model complexes for nitrogenase, compounds with the [Ru(PiPr(3))('N(2)Me(2)S(2)')] fragment were found ('N(2)Me(2)S(2)'(2-)=1,2-ethanediamine-N,N'-dimethyl-N,N'-bis(2-benzenethiolate)(2-)). This fragment enabled the synthesis of a first series of chiral metal sulfur complexes, [Ru(L)(PiPr(3))('N(2)Me(2)S(2)')] with L=N(2), N(2)H(2), N(2)H(4), and NH(3), that meet the biological constraint of forming under mild conditions. The reaction of [Ru(NCCH(3))(PiPr(3))('N(2)Me(2)S(2)')] (1) with NH(3) gave the ammonia complex [Ru(NH(3))(PiPr(3))('N(2)Me(2)S(2)')] (4), which readily exchanged NH(3) for N(2) to yield the mononuclear dinitrogen complex [Ru(N(2))(PiPr(3))('N(2)Me(2)S(2)')] (2) in almost quantitative yield. Complex 2, obtained by this new efficient synthesis, was the starting material for the synthesis of dinuclear (R,R)- and (S,S)-[micro-N(2)[Ru(PiPr(3))('N(2)Me(2)S(2)')](2)] ((R,R)-/(S,S)-3). (Both 2 and 3 have been reported previously.) The as-yet inexplicable behavior of complex 3 to form also the R,S isomer in solution has been revealed by DFT calculations and (2)D NMR spectroscopy studies. The reaction of 1 or 2 with anhydrous hydrazine yielded the hydrazine complex [Ru(N(2)H(4))(PiPr(3))('N(2)Me(2)S(2)')] (6), which is a highly reactive intermediate. Disproportionation of 6 resulted in the formation of mononuclear diazene complexes, the ammonia complex 4, and finally the dinuclear diazene complex [micro-N(2)H(2)[Ru(PiPr(3))('N(2)Me(2)S(2)')](2)] (5). Dinuclear complex 5 could also be obtained directly in an independent synthesis from 1 and N(2)H(2), which was generated in situ by acidolysis of K(2)N(2)(CO(2))(2). Treatment of 6 with CH(2)Cl(2), however, formed a chloromethylated diazene species [[Ru(PiPr(3))('N(2)Me(2)S(2)')]-micro-N(2)H(2)[Ru(Cl)('N(2)Me(2)S(2)CH(2)Cl')]] (9) ('N(2)Me(2)S(2)CH(2)Cl'(2-) =1,2-ethanediamine-N,N'-dimethyl-N-(2-benzenethiolate)(1-)-N'-(2-benzenechloromethylthioether)(1-)]. The molecular structures of 4, 5, and 9 were determined by X-ray crystal structure analysis, and the labile N(2)H(4) complex 6 was characterized by NMR spectroscopy. 相似文献
92.
Qing-Shan Li Juan-Juan Xu Jian-Jiang Zhong 《Applied biochemistry and biotechnology》1997,62(2-3):243-250
Effects of water content and carbon and nitrogen sources on the production ofL-glutamate oxidase (GOD) by solid state fermentation (SSF) ofStreptomyces sp. N1 were investigated in a 250-mL shake flask. The results show that in the solid medium containing wheat bran 98% (w/w), KCl
0.2% (w/w), and MgCl2 0.2% (w/w), addition of 2.0-mL water per gram solid medium and 0.4% (w/w) (NH4)2SO4 was the best for GOD production. In this work, we also developed a simple technique forin situ measuring oxygen uptake rate (OUR) and carbon dioxide evolution rate (CER) in SSF in a shake flask based on the principle
of Warburg manometer. The method was successfully applied to determine OUR and CER values in SSF ofStreptomyces sp. N1. The results indicate that the largest OUR value was detected about one or two days ahead of the highest GOD activity reached
depending on the fermentation conditions, and the OUR may be used as anin situ indicator of GOD production in the SSF process. 相似文献
93.
诱导效应指数与含硫含氮的低碳直链有机化合物的标准汽化热 总被引:2,自引:0,他引:2
本文利用诱导效应指数建立了含硫含氮的低碳直链有机物的标准汽化热的简单估算方法,我们利用此法计算了一些含硫含氮的直链有机物的标准汽化热,41个可比较值的相对误差均在5%以内。 相似文献
94.
Kristian Lappalainen Katariina Yliheikkil Adnan S. Abu‐Surrah Mika Polamo Markku Leskel Timo Repo 《无机化学与普通化学杂志》2005,631(4):763-768
Iron(II) and cobalt(II) complexes ( 7 ‐ 15 ) based on new aldimine 2, 6‐bis[(imino)methyl]pyridine ( 1 , 2 , 4 , 6 ) and ketimine (2, 6‐bis[(imino)ethyl]pyridine ( 3 , 5 ) ligands with bulky chiral aliphatic or aromatic terminal groups have been prepared and characterized by 1H NMR, 13C NMR, IR‐, mass spectroscopy (EI), and elemental analysis. The complex [CoCl2(BBoMP)]·1/2 CHCl3 ( 13 ) (BBoMP: 2, 6‐bis{(R‐(+)‐(bornylimino)‐methyl}pyridine) crystallizes in monoclinic space group P21 with cell dimensions: a = 7.6603(11) Å, b = 28.3153(14) Å, c = 13.537(2) Å, V = 2908.1(6) Å3, Z = 4. The coordination sphere around Co is distorted trigonal bipyramidal. 相似文献
95.
Studt F MacKay BA Johnson SA Patrick BO Fryzuk MD Tuczek F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(2):604-618
Reaction of the side-on end-on dinitrogen complex [{(NPN)Ta}(2)(mu-H)(2)(mu-eta(1):eta(2)-N(2))] (1; in which NPN=(PhNSiMe(2)CH(2))(2)PPh), with the Lewis acids XR(3) results in the adducts [{(NPN)Ta}(2)(mu-H)(2)(mu-eta(1):eta(2)-NNXR(3))], XR(3)=GaMe(3) (2), AlMe(3) (3), and B(C(6)F(5))(3) (4). The solid-state molecular structures of 2, 3, and 4 demonstrate that the N-N bond length increases relative to those found in 1 by 0.036, 0.043, and 0.073 A, respectively. In solution complexes 2-4 are fluxional as evidenced by variable-temperature (1)H NMR spectroscopy. The (15)N{(1)H} NMR spectra of 2-4 are reported; furthermore, their vibrational properties and electronic structures are evaluated. The vibrational structures are found to be closely related to that of the parent complex 1. Detailed spectroscopic analysis on 2-4 leads to the identification of the theoretically expected six normal modes of the Ta(2)N(2) core. On the basis of experimental frequencies and the QCB-NCA procedure, the force constants are determined. Importantly, the N-N force constant decreases from 2.430 mdyn A(-1) in 1 to 1.876 (2), 1.729 (3), and 1.515 mdyn A(-1) (4), in line with the sequence of N-N bond lengths determined crystallographically. DFT calculations on a generic model of the Lewis acid adducts 2-4 reveal that the major donor interaction between the terminal nitrogen atom and the Lewis acid is mediated by a sigma/pi hybrid molecular orbital of N(2), corresponding to a sigma bond. Charge analysis performed for the adducts indicates that the negative charge on the terminal nitrogen atom of the dinitrogen ligand increases with respect to 1. The lengthening of the N-N bond observed for the Lewis adducts is therefore explained by the fact that charge donation from the complex fragment into the pi* orbitals of dinitrogen is increased, while electron density from the N-N bonding orbitals p(sigma) and pi(h) is withdrawn due to the sigma interaction with the Lewis acid. 相似文献
96.
Kraft S Hanuschek E Beckhaus R Haase D Saak W 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(3):969-978
This paper reports on the potential of titanium compounds as building blocks for supramolecular polygons. Self-assembly reactions of low-valent titanocene units and N-heterocyclic bridging ligands lead to novel titanium-based supramolecular squares. Pyrazine (3), 4,4'-bipyridine (4), and tetrazine (5) were used as bridging ligands, and the acetylene complexes [Cp2Ti{eta2-C2(SiMe3)2}] (1) and [(tBuCp)2Ti{eta2-C2(SiMe3)2}] (2) as sources of titanocene fragments. Molecular rectangles can be synthesized by stepwise reduction of the titanocene dichlorides [Cp(2)TiCl2] and [(tBuCp)2TiCl2] and consecutive coordination of two different bridging ligands. The resulting complexes are the first examples of molecular rectangles containing bent metallocene corner units. Single-crystal X-ray analyses of the tetranuclear compounds revealed the geometric properties of the molecular polygons in the solid state. Comparison of bond lengths and angles in coordinated and free ligands reveals the reduced state of the bridging ligand in the low-valent titanium compounds. The syntheses and properties of these novel, highly air- and moisture-sensitive compounds are discussed. 相似文献
97.
Soncini A Domene C Engelberts JJ Fowler PW Rassat A van Lenthe JH Havenith RW Jenneskens LW 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(4):1257-1266
Why are some (4n+2)π systems aromatic, and some not? The ipsocentric approach to the calculation of the current density induced in a molecule by an external magnetic field predicts a four‐electron diatropic (aromatic) ring current for (4n+2)π carbocycles and a two‐electron paratropic (antiaromatic) current for (4n)π carbocycles. With the inclusion of an electronegativity parameter, an ipsocentric frontier‐orbital model also predicts the transition from delocalised currents in carbocycles to nitrogen‐localised currents in alternating azabora‐heterocycles, which rationalises the differences in (magnetic) aromaticity between these isoelectronic π‐conjugated systems. Ab initio valence‐bond calculations confirm the localisation predicted by the naïve model, and coupled‐Hartree–Fock calculations give current‐density maps that exhibit the predicted delocalised‐to‐localised/carbocycle–heterocycle transition. 相似文献
98.
《Surface and interface analysis : SIA》2005,37(9):737-742
A novel method that allows the determination of the electrical potential of a polymer surface has been applied for polypropylene film treated by N2 + H2 cold plasma. The plasma treatment results in formation on the film surface of NH2 groups, which then gets transformed to NH3+ in contact with an electrolyte and leads to the formation of an electrical double layer. The method consists of theoretical calculation of electrical model potential, using the measurement of the electrical capacitance of the film in contact with an electrolyte by dielectric spectroscopy. Comparison with the results obtained by theoretical model shows similar dependencies of the electrical potential as a function of amino‐groups density and electrolyte concentration, but systematic differences of absolute values are observed. Copyright © 2005 John Wiley & Sons, Ltd. 相似文献
99.
Clean-up and analysis of carbazole and acridine type polycyclic aromatic nitrogen heterocyclics in complex sample matrices 总被引:1,自引:0,他引:1
A HPLC method for the analysis of polycyclic aromatic nitrogen heterocyclics (PANHs) in complex sample matrices is presented. It isolated and separated carbazole and acridine type PANHs with an absolute recovery of between 79–98%. Open column chromatography is used as an initial step to isolate a PANH fraction. By applying normal-phase liquid chromatography using a dimethylaminopropyl silica stationary phase and utilising back-flush technique it was possible to separate the PANH fraction into two fractions containing acridine type and carbazole type PANHs, respectively. The method applied on a sample of solvent refined coal heavy distillate (SRC II HD). A number of 3–5 ring acridines and carbazoles were identified with GC–electron impact MS and quantified with GC–nitrogen–phosphorous detection. Polycyclic aromatic hydrocarbons (PAHs) were determined in the SRC II HD sample by automated on-line clean-up and analysis of the obtained PAH fraction with coupled LC–GC–flame ionization detection. There was no overlap between the PANH and the PAH fractions with this method, and carbazoles and acridines were efficiently separated. 相似文献
100.
3-[1′(1′H)-Substituent-pyrazol-5′-yl]benzo[5,6]coumarins and 3-(1′,2′-oxazol-5′-yl)benzo[5,6]coumarin were prepared via condensation of 3-(2′-formyl-1′-chlorovinyl)benzo[5,6] coumarin with hydrazine derivatives or hydroxylamine.Reaction of 3-[1′(1′H)-pyrazol-5′-yl]benzo[5,6]coumarin with alkyl halides,olefinic compunds or acid chlorides are described. 相似文献