Category: 14187-32-7

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Dianionic Mononuclear Cyclo-P4 Complexes of Zero-Valent Molybdenum: Coordination of the Cyclo-P4 Dianion in the Absence of Intramolecular Charge Transfer

Relative to other cyclic poly-phosphorus species (that is, cyclo-Pn), the planar cyclo-P4 group is unique in its requirement of two additional electrons to achieve aromaticity. These electrons are supplied from one or more metal centers. However, the degree of charge transfer is dependent on the nature of the metal fragment. Unique examples of dianionic mononuclear eta4-P4 complexes are presented that can be viewed as the simple coordination of the [cyclo-P4]2? dianion to a neutral metal fragment. Treatment of the neutral, molybdenum cyclo-P4 complexes Mo(eta4-P4)I2(CO)(CNArDipp2)2 and Mo(eta4-P4)(CO)2(CNArDipp2)2 with KC8 produces the dianionic, three-legged piano stool complexes, [Mo(eta4-P4)(CO)(CNArDipp2)2]2? and [Mo(eta4-P4)(CO)2(CNArDipp2)]2?, respectively. Structural, spectroscopic, and computational studies reveal a similarity to the classic eta6-benzene complex (eta6-C6H6)Mo(CO)3 regarding the metal-center valence state and electronic population of the planar-cyclic ligand pi system.

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Transition-metal Complexes of Crown Ether Benzodithiolenes

Three new dithiolene ligands have been synthesized, two of which have the novel feature of a crown ether ring attached directly to the benzene ring of an aryl dithiolene.Complexes with transition metals have been prepared and their (1)H, (13)C NMR, UV/VIS and electrochemical properties recorded.The information obtained appears to reflect variations in the degree of delocalisation in the metallodithiolene ring within the series of complex types.

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The Solvent Extraction Study of a Dibenzo-18-crown-6 Complex with Silver Picrate

The extraction constant of the silver ion-dibenzo-18-crown-6 (DB18C6) complex between benzene and water and the complex-formation constant of DB18C6 with silver picrate in benzene were determined at 25 deg C.The Ag+-DB18C6 complex is much more extractable than the Ag+-18-crown-6 one.The Ag+-DB18C6 complex is much more stable for benzene than for aqueous solutions.

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Pseudorotaxane based on tetraazamacrocyclic copper complex and dibenzocrown ether

Host-guest interactions between two electron-rich dibenzocrown ethers and electron deficient macrocyclic copper(ii) tetraimine complexes lead to the formation of pseudorotaxane in solution. The interactions are enhanced with the copper(iii) complex compared to that of the copper(ii) form as shown by the electrochemical studies. The larger – 30-membered dibenzocrown donor interacted with the copper complex stronger than the smaller ones as revealed by NMR and electrochemical methods. The thiolated form of the copper(ii) tetraimine complex was self-assembled at the gold electrode forming an electroactive monolayer able to interact with the crown ether in the solution. These donor-acceptor interactions lead to an increase of the barrier properties of the layer and decreased the electron transfer rate between the copper centre and the gold electrode surface as proved by the voltammetric data.

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Synthesis, crystal structure and NMR of [Na(DB18C6)(CH3CN)] 3[alpha-AsM12O40] (M = Mo/W)

Two super-molecular complexes [Na(DB18C6)(CH3CN)] 3[alpha-AsM12O40] (M = Mo/W) were obtained by solvothermal reaction and characterized by IR,1H 13C and gUMBC NMR, X-ray. The result reveals that the complex consists of a [alpha-AsM12O40]3- (M = Mo/W) anion with alpha-Keggin structure, and three complex [Na (DB18C6)(CH3CN)] + cations in which every sodium ion is located in the cavity of dibenzo-18-crown-6 with 6 Na-O bonds and coordinated with one of the terminal O atom of [alpha-AsM12O40]3- (M = Mo/W) and the N atom of CH3CN from two sides of the distorted DB18C6 plane, respectively. The three terminal O atoms linked with sodium ion are from a single M3O13 (M = Mo/W) triplet of the alpha-Keggin metalatoarsenate anion, and M-Ob (M = Mo/W) bonds exhibit alternating single-double bond character.

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Application of 14187-32-7. Let¡¯s face it, organic chemistry can seem difficult to learn. Especially from a beginner¡¯s point of view. Like 14187-32-7, Name is Dibenzo-18-crown-6. In a document type is Conference Paper, introducing its new discovery.

Synthesis, crystal structure and NMR of [Na(DB18C6)(CH3CN)] 3[alpha-PW12O40]

A novel super-molecular complex [Na(DB18C6)(CH3CN)]3 [alpha-PW12O40] was obtained by solvothermal reaction and characterized by IR, X-ray, 1H, 13C and 31P NMR. The result reveals that the complex consists of an [alpha-PW 12O40]3- anion with alpha-Keggin structure and three complex [Na(DB18C6)(CH3OH)]+ cations in which every sodium ion located in the cavity of dibenzo-18-crown-6 with six Na-O bonds and coordinated with one of the terminal O atom of [alpha-PW 12O40]3- and the N atom of CH3CN from two sides of the distorted DB18C6 plane, respectively. The three terminal O atoms linked with sodium ion are from a single W3O3 triplet of the alpha-Keggin tungstophosphate anion. The 13C resonance (119.27 ppm) bonded to N atom in CH3CN has been clarified by gUMBC spectrum (see Fig. 1), which is too weak to be observed in 13C NMR spectrum due to its too low relaxation rate.

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Mechanism of Complexation of Crown Ethers as a Function of Alkali Ions and the Rigidity of the Ligands

The kinetics of complexation of Na+ and K+ with the crown ethers dicyclohexano-18-crown-6 (DH18C6) and dibenzo-18-crown-6 (DB18C6) in the solvent dimethylformamide (DMF) and Na+ with DH18C6 in methanol (MeOH) have been studied by ultrasonic relaxation techniques in the frequency range from <*>1 to <*>400 MHz.The results are compared with data for the same cations reacting with 18-crown-6 (18C6).In DMF at 40 deg C for Na+ added to DH18C6 in molar ratio R <*> 1 two relaxation processes apper that are displaced within a factor of two in relaxation frequencies from those of the system Na+ = 18C6.For K+ added to DH18C6 (R=1) two relaxation processes appear at about the same frequency as for the system K+ + 18C6.The difference between the results for Na+ and K+ may reflect the closer fit of the potassium cation radius with the macrocycle cavyty.For Na+ + DB18C6 in DMF at 40 deg C two relaxation processes, the first at about the same frequency as for DH18C6 but the second below 1 MHz, are detectable.For K+ + DB18C6 in DMF at 40 deg C, both relaxation frequencies are dramatically shifted with the lower one lying below 1 MHz.The behavior of the process at lower frequency is compatible with the progressive increase of ligand ring rigidity in going from 18C6 to DH18C6 and to DB18C6, if the rate-determining factor of the process at the lower frequency is attributed to the encirclement of the metal cation by the ligand.In MeOH the surmise that the ligand rearrangement also plays a role in the reaction coordinate energy profile of the complexation of alkali metal cations added to 18C6 is supported by new data now available with the resonator technique, the data revealing two relaxation processes for both Li+ and Na+.In MeOH, the system Na+ + DH18C6 gives rise to two detectable relaxation processes at 25 deg C.Surprisingly, they are a factor of two faster than for the system Na+ + 18C6 (at variance with the same system in DMF solvent).For Li+ + DH18C6 in MeOH from the only run available it appears that the process at high frequency is somewhat faster than for Li+ + 18C6 in MeOH whereas the one at low frequency is lower by a factor of 3 or more with respect to the one in the system Li+ + 18C6.This complex behavior may indicate a concerted process in which both the solvent substitution and ligand rearrangement influence the energy profile of the overall process.In the majority of cases the activation parameters have been evaluated from the temperature dependence of the relaxation processes.

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The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.14187-32-7, Name is Dibenzo-18-crown-6, molecular formula is C20H24O6. In a Article£¬once mentioned of 14187-32-7, Formula: C20H24O6

Second-sphere Co-ordination of Cationic Rhodium Complexes (Rh(L)(NH3)2)+ by Dibenzo-3n-crown-n Ethers . Solution 1H Nuclear Magnetic Resonance Spectroscopic Studies and X-Ray Crystal Structures

Cationic rhodium(1) complexes of the form are solubilised in halocarbon solvents by the addition of equimolar quantities of crown ethers such as 18-crown-6 (18-c-6) or dibenzo-3n-crown-n (n=6-12) ethers (db-3n-c-n).Solubilisation is a result of the formation of stable, highly structured, second-sphere co-ordination complexes in which a macrocyclic polyether interacts with the ammine ligands on rhodium via multiple hydrogen-bond formation. 1H N.m.r. spectroscopic investigations in CD2Cl2 show that the resonances of protons associated with the diene ligands (L) undergo significant upfield shifts (Deltadelta values of up to 0.75 p.p.m.) when certain of the db-3n-c-n ethers (n=7-10) are used in preference to 18-c-6, suggesting that the dienes are experiencing anisotropic ring-current shielding by the crown ether benzo rings.The close proximity of co-ordinated diene and db-3n-c-n ether aromatic rings, which this shielding requires, is confirmed by single-crystal X-ray studies of the isolated 1:1 adducts. (Rh(cod)(NH3)2.db-21-c-7> is monoclinic, space group P21/c,a=9.121(1), b=23.405(2), c=16.705(3) Angstroem, beta=96.30(1) deg, Z=4, R=0.047. is monoclinic, P21/c,a=9.195(3), b=29.380(9), c=13.900(6) Angstroem, beta=93.04(3) deg, Z=4, R=0.043. is monoclinic, P21/c,a=9.268(2), b=34.335(7), c=13.421(3) Angstroem, b=93.92(2) deg, Z=4, R=0.034. is orthorombic, Pbca,a=15.427(3), b=18.739(3), c=25.458(5) Angstroem, Z=8, R=0.047.In all these supramolecular structures the crown ether adopts a V-shaped conformation with the ammine ligands forming hydrogen bonds to ether oxygens and with the co-ordinated diene sandwiched between the benzo rings of the db-3n-c-n ethers.In the addition to electrostatic stabilisation, there are also a large number of other longer range contacts (C…H, Rh…C, Rh…O) at about van der Waals’ distances which probably make a small contribution to the binding energy and possibly help to define the structures of the adducts.In contrast to the 1:1 adducts, the 2:1 adduct, <2.db-36-c-12>2 (triclinic, P1*, a=9.020(2), b=12.241(3), c=14.196(3) Angstroem, alpha=100.20(2), beta=99.00(2), gamma=98.11(2) deg, Z=1, R=0.040) has a relatively flat structure in which a complex ion is hydrogen bonded to each face of the crown ether.

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The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.14187-32-7, Name is Dibenzo-18-crown-6, molecular formula is C20H24O6. In a Article£¬once mentioned of 14187-32-7, Quality Control of: Dibenzo-18-crown-6

Synthesis of Azo Dyes from Mesoionic Carbenes and Nitrous Oxide

Covalent adducts of imidazole-based mesoionic carbenes and nitrous oxide (N2O, ?laughing gas?) can be converted into azo dyes by reaction with arenes in the presence of AlCl3 or HCl. The azo coupling can be achieved with electron-rich aromatic compounds such as mesitylene, trimethoxybenzene, azulene, or dibenzo-18-crown-6. The latter coupling reaction allows for the easy preparation of a colorimetric sensor for potassium or sodium ions. As a putative intermediate of the reaction with acid, we were able to isolate and structurally characterize a rare diazohydroxide. Using imidazolium compounds with two N2O groups, it was possible to prepare amine-substituted azo dyes or dyes with two azoarene groups attached to the heterocycle. A triazole-based mesoionic carbene was also found to form a stable covalent adduct with N2O. The adduct could be used to prepare novel azo triazolium dyes in good yields.

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The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.14187-32-7, Name is Dibenzo-18-crown-6, molecular formula is C20H24O6. In a Article£¬once mentioned of 14187-32-7, Recommanded Product: Dibenzo-18-crown-6

The influence of structural effects on the complexing ability of crown ethers. III. Rubidium complexes formed by the ligands of the 18C6 type

A combined AM1 and molecular mechanics study of the complexation of the rubidium cation by nine substituted crown ethers, L, containing 18 atoms of macroring is presented. The role of microsolvation was incorporated into the models by studying the complexes surrounded by six methanol molecules. The substituent effect is related to the interaction energy, Eint, which was computed for the clusters LRb+(CH3OH)6 in their lowest energy conformations. This is demonstrated by the linear correlation found by plotting log Ks vs. Eint, where K2 stands for stability constant of a complex. The appropriate Ks values were calculated on the basis of cyclic voltammetric measurements.

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