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1.
The complexes (2RCu · MX) between 2-(dimethylamino)phenylcopper (RCu) and CuX (X = Cl, Br or I) or AgBr have been prepared in two ways (i) from the reaction of 2-(dimethylamino)phenyllithium with cuprous halide and (ii) from the reaction of RCu with excess of the metalIB halide.The structure of bis[(2-dimethylamino)phenylcopper] cuprous bromide, which is dimeric (R4Cu6Br2) in the solid state, has been determined by X-ray analysis. The bonding in this hexanuclear cluster (CuCu ranging from 2.48 to 2.70 Å, multicenter bonded aryl groups) is discussed. Molecular weight determinations and 1H NMR spectroscopy reveal a similar hexanuclear structure for the R4Cu6X2 complexes in benzene solution. NMR spectroscopy indicates that in solution the mixed-metal cluster compounds R4Cu6-nAgnBr2 are not stable but enter into interaggregate exchange reactions. A possible pathway involving trinuclear species R2Cu3-nAgnX as intermediates is proposed. 相似文献
2.
The synthesis and isolation of 2-[(dimethylamino)methyl]phenylcopper and its 5-methyl, 5-methoxy, 5-chloro and 3-chloro derivatives are described. These hydrocarbon-soluble arylcopper compounds are appreciably more thermally stable than phenylcopper (e.g. 2-[(dimethylamino)methyl]phenylcopper decomposes only at 175–185°). They also show improved hydrolytic and oxidative stability.Lithiation of 1-methoxy-4-[(dimethylamino)methyl]naphthalene with butyllithium occurs at the 5-position. Metathesis of 1-methoxy-4-[(dimethylamino)methyl]-5-lithionaphthalene with cuprous bromide affords the corresponding organocopper compound. 相似文献
3.
Reaction of Me5C5Li and Ni(CO)4 gave [(n5-Me5C5)Ni(CO)]2 () in 40 % yield. Reaction of with iodine followed by addition of a tertiary phosphine or reaction of (PPh3)2NiX2 with Me5C5Li or Me5C5SnBu3 gave (n5-Me5C5)Ni(L)X () (L = tertiary phosphine, X = halogen). Treatment of with RLi (R = Me, PhCC) afforded (n5-Me5C5)Ni(L)R (). The spectroscopic properties and the reactivities of n5-pentamethylcyclopentadienylnickel complexes indicate that the n5-Me5C5 ligand is more electron-donating and a sterically more bulky than the n5-C5H5 ligand. 相似文献
4.
Rajendiran Thekkel M. Kannappan Ramu Mahalakshmy Rajaram Rajeswari Janarthanam Venkatesan Rangarajan Rao Pillutla 《Transition Metal Chemistry》2003,28(4):447-454
A series of binuclear CuII complexes [Cu2XL]
n+ having two copper(II) ions bridged by different motifs (X = OH–, MeCO2
–, or Cl–) have been prepared using the ligands: H2L1 = 4-methyl-2-[N-(2-{dimethylamino}ethyl-N-methyl)aminomethyl]-6-[(prolin-1-yl)methyl]phenol, H2L2 = 4-nitro-2-[N-(2-{dimethylamino}ethyl-N-methyl)aminomethyl]-6-[(prolin-1-yl)methyl]phenol, H2L3 = 4-methyl-2-[N-(2-{diethylamino}ethyl-N-ethyl)aminomethyl]-6-[(prolin-1-yl)methyl]phenol and H2L4 = 4-nitro-2-[N-(2-{diethylamino}ethyl-N-ethyl)aminomethyl]-6-[(prolin-1-yl)methyl]phenol. The complexes have been characterized by spectroscopic, analytical, magnetic and electrochemical measurements. Cryomagnetic investigations (80–300 K) revealed anti-ferromagnetic exchange between the CuII ions (–2J in the range –50 to –182 cm–1). The strength of anti-ferromagnetic coupling lies in the order: OAc > OH > Cl. Cyclic voltammetry revealed the presence of two redox couples, assigned to CuII/CuII/CuII/CuI/CuI/CuI. The first reduction potential is sensitive to electronic effects from the aromatic ring substituents and steric effect on the donor nitrogens (side arm) of the ligand systems. 相似文献
5.
Copper(I), copper(II), and thallium(III) hexafluoromolybdates(V), prepared by the oxidation of the metals in acetonitrile with molybdenum hexafluoride (A. Prescott, D.W.A.Sharp, and J.M. Winfield, , 1975, 963) have been investigated by cyclic voltametry. Half wave potentials, E V vs. Agp+/Ag were obtained using a evacuable cell equipped with anexternal Agp+/Ag electrode, enabling strict anerobic conditions to be maintained. A number of reversible or quasi-reversible electron transfer processes have been observed, enabling comparison with synthetic work to be made. Results for CuI and CuII hexafluoromolybdates(V) are in accord with preparative experience. MoF6. MoVI/MoVE +1.600V, oxidises Cu metal to CuII in MeCN, and CuII is reduced by CuO to CuI , CulI/CuIE = +0.750 or +0.710V for CuI and CuII solutes respectively, CuI/CuOE = ?0.720V not reversible. A wave at E = ?0.350V is assigned to MoV/MoIV by analogy with AgI hexafluoromolybdate (D.W.A. Sharp, unpublished work). E data for I2 in MeCN, I2/I3- = 0.280, I3?/I? = -0.116V, suggest that reduction of MoF6? by I is not likely, in contrast to the situation in SO2 (A.J. Edwards and R.D. Peacock, , 1960, 1441). Reduction of MoF6? by Cuo in MeCN should be feasible, but appears to be very slow. Pure TλIII hexafluoromolybdate(V) is obtained from Tλo and MoF6 only when the mole ratio MoF6:Tλ>5:1. Smaller ratios produce yellow solids in which Mo:Tλ is . 2:1. TλIII is a stronger oxidising agent than CuII in MeCN, as oxidation of CuI by TλIII is rapid and quantitative. However a reversible electron transfer wave assignable to TλIII/TλI is not observed in the expected fange +1.600 to +0.710V possibly because of solute-electrode interactions. 相似文献
6.
A series of oxygen-defect perovskites, containing CuII and CuIII, La3Ba3 [CuII5?2y CuIII1+2y] O14+y, has been synthesized at 1000°C, for 0.05 ≤ y ≤ 0.43. The substitution of lanthanum for yttrium and lanthanides has been studied. These oxides are tetragonal: and c = 3ap. The structural study of La3Ba3 Cu6O14.10 shows that oxygen vacancies are ordered, involving for copper three sorts of coordination: square, pyramidal (4 + 1), and distorted octahedral (4 + 2). The distribution of CuIII, as well as the lanthanide ions on the different sites, is discussed. 相似文献
7.
Asymmetric cyclizations of methyl (E)-3-oxo-9-phenoxy-7-nonenoate () or methyl (E)-3-oxo-9-(methoxycarbonyl)oxy-7-nonenoate () without added base were carried out in the presence of a catalytic amount of palladium(II) acetate and chiral diphosphine as ligands. Allylic carbonate reacted by use of Pd(OAC)2-(S)-(R)-BPPFA at room temperature to give (R)-3-vinylcyclohexanone (), after decarboxylation, in up to 48% e. e. 相似文献
8.
tert-Butyl azidoformate () reacts with the conjugate bases of , , (R1 = R2 = CH3), and (R1 = CH3, R2 = H) to give products [, , , and , respectively] in addition to the expected N-(tert-butoxycarbonyl)indole derivatives. 相似文献
9.
From the study of the CuCuBrCu2?εSC solid cell in the range of cubic digenite and “high temperature” hexagonal chalcocite we have deduced the laws of variation of the deviation from stoichiometry and the holes concentration with the equilibrium partial pressure of sulfur (δ and p are found to be proportional to ). The electronic model corresponding to the formation of associations (V×CuV′Cu) in the presence of neutral vacancies V×Cu allows one to explain these laws. In the low temperature range (range of “low temperature” hexagonal chalcocite and orthorhombic chalcocite) the study of thermal variations of Hall coefficient permits us to propose the following models: (a) the deviation from stoichiometry of the “low temperature” hexagonal chalcocite is due to the simple ionized vacancies V′Cu; (b) the deviation from stoichiometry of the orthorhombic chalcocite is due to the vacancies V′Cu and to the associations (V×CuV×Cu). 相似文献
10.
When the trimethyl derivatives of aluminium, gallium and indium react with glyoximato metallates, (R2C2N2(O)OH)2MetII (R = H, CH3; MetII = Ni, Pd, Pt, Cu), in a molar ratio, 2 mol of methane are evolved and monomeric bis(dimethylmetal(III)glyoximato)metallates(II) (metal(III) = Al, Ga, In) are formed in high yields. The vibrational and NMR spectra of the new complexes were measured and were partly resolved. The X-ray structure determinations of two of these compounds show non-planar structures of approximate C2h and C2 symmetry, respectively, with weak metal(III)?metal(II) π-interactions. 相似文献
11.
The crystal structure of a second high-pressure copper vanadate phase, CuVO3(II), has been determined and refined by full-matrix least-squares procedures using automatic diffractometer data to a residual R = 0.042 (Rw = 0.051). The space group is rhombohedral, , with hexagonal unit cell a = 4.966(2) and c = 14.084(5) Å [aR = 5.501(2) Å and α = 53.66(3)°]. The structure is the fully ordered ilmenite-type and, on the basis of published magnetic data and the interatomic distances, the valence distribution Cu+V5+O3 is proposed. This represents a unique example of Cu+ in an octahedral environment. 相似文献
12.
Novel monomeric benzyl- and aryl-gold(I) triphenylphosphine complexes have been prepared. Pure, uncomplexed 2-[(dimethylamino)methyl]-phenylgold(I) has been isolated from the reaction of tetranuclear bis {2-[(dimethylamino)methyl]phenyl}goldlithium (R4 Au2 Li2) with trimethyltin bromide. 相似文献
13.
Youhei ShimogoriTakefumi Hamamatsu Takeshi FujinamiHiroaki Hagiwara Naohide Matsumoto Nazzareno ReJerzy Mrozinski Yuichi IshikawaAsako Igashira-Kamiyama Takumi Konno 《Polyhedron》2011,30(6):1127-1133
A linear tetranuclear CuII-GdIII-CuII-GdIII complex [CuIILdpen(meso)GdIII(thd)2(H2O)]2 was synthesized from the reaction of [NaCuIILdpen(meso)(DMF)] with [GdIII(thd)3(H2O)2], and the structures and magnetic properties were investigated, where H3Ldpen(meso) = meso-1,2-diphenyl-1-(2-hydroxybenzamido)-2-(2-hydroxy-3-ethoxybenzylideneamino)ethane and Hthd = 2,2,6,6-tetramethyl-3,5-heptanedione. The CuII complex component [NaCuIILdpen(meso)(DMF)] has a one-dimensional (1D) chain structure, in which the Na+ ion is coordinated by two phenoxo and an ethoxy oxygen atoms of a CuII complex and an amido oxygen atom of the adjacent CuII unit to produce the 1D structure, in which the diphenylethylenediamine moieties have the array of {(1R,2S)-Na-(1S,2R)}1∞. The assembly reaction of the CuII and GdIII components gave a linear complex with the array of Cu(1)-Gd(1)-Cu(2)-Gd(2), in which two diphenylethylenediamine moieties have the same chirality of (1R,2S)-(1R,2S) or (1S,2R)-(1S,2R). Two linear Cu(1)-Gd(1)-Cu(2)-Gd(2) units are linked by hydrogen bonds through two water molecules to give a cyclic structure with a center of symmetry. The temperature dependence of the magnetic susceptibilities and field-dependent magnetization revealed the ferromagnetic interaction between the CuII and GdIII ions within the linear chain. 相似文献
14.
T. Tanaka N. Okamura K. Bannai A. Hazato S. Sugiura K. Manabe S. Kurozumi 《Tetrahedron letters》1985,26(45):5575-5578
(5)-Prostaglandin E2 methyl ester was synthesized from ()-4--butyldimethylsiloxy-2-cyclopentenone by 2-alkenyloxycarbonylation of the organocopper conjugate-addition adduct followed by intramolecular palladium-catalyzed decarboxylative 2-alkenylation. A ()-2-butenylated cyclopentanone derivative was obtained from either 2-[()- or ()-2-butenyloxy-carbonyl]cyclopentanone derivative under the similar reaction condition. 相似文献
15.
A. V. Lobanov E. N. Golubeva E. M. Zubanova M. Ya. Mel’nikov 《High Energy Chemistry》2009,43(5):384-390
The product composition and the principles of photochemical transformations of tetrahexylammonium tetrachlorocuprate [(RH)4N+]2[CuIICl4]2− (RH = C6H13) in 2-chlorobutane at 77 K have been found out by ESR spectroscopy. It has been shown that the photolysis of [(RH)4N+]2 [CuIICl4]2− results in the formation of alkyl radicals (R⊙), presumably, anions [CuICl3]2− and organic copper(II) compounds {CuIIR}. A reduction in the quantum yield of primary photolysis products during the reaction, nonequivalence of the quantum yield
of the buildup of paramagnetic photolysis products to that of [CuIICl4]2− consumption, and a decrease in the total number of paramagnetic particles in the system during the photolysis have been revealed.
A photolysis mechanism involving both photochemical and thermal processes is proposed. 相似文献
16.
Anand Gupta Rajesh Deka Ray J. Butcher Harkesh B. Singh 《Acta Crystallographica. Section C, Structural Chemistry》2020,76(8):828-835
The intramolecularly coordinated homoleptic diorgano selenide bis{2,6‐bis[(dimethylamino)methyl]phenyl} selenide, C24H38N4Se or R2Se, where R is 2,6‐(Me2NCH2)2C6H3, 14 , was synthesized and its ligation reactions with PdII and HgII precursors were explored. The reaction of 14 with SO2Cl2 and K2PdCl4 resulted in the formation of the meta C—H‐activated dipalladated complex {μ‐2,2′‐bis[(dimethylamino)methyl]‐4,4′‐bis[(dimethylazaniumyl)methyl]‐3,3′‐selanediyldiphenyl‐κ4C1,N2:C1′,N2′}bis[dichloridopalladium(II)], [Pd2Cl4(C24H38N4Se)] or [{R(H)PdCl2}2Se], 15 . On the other hand, when ligand 14 was reacted with HgCl2, the reaction afforded a dimercurated selenolate complex, {μ‐bis{2,6‐bis[(dimethylamino)methyl]benzeneselanolato‐κ4N2,Se:Se,N6}‐μ‐chlorido‐bis[chloridomercury(II)], [Hg2(C12H19N2Se)Cl3] or RSeHg2Cl3, 16 , where two HgII ions are bridged by selenolate and chloride ligands. In palladium complex 15 , there are two molecules located on crystallographic twofold axes and within each molecule the Pd moieties are related by symmetry, but there are still two independent Pd centers. Mercury complex 16 results from the cleavage of one of the Se—C bonds to form a bifurcated SeHg2 moiety with the formal charge on the Se atom being ?1. In addition, one of the Cl ligands bridges the two Hg atoms and there are two terminal Hg—Cl bonds. Each Hg atom is in a distorted environment which can be best described as a T‐shaped base with the bridging Cl atom in an apical position, with several angles close to 90° and with one angle much larger and closer to 180°. 相似文献
17.
18.
The rate of the thermal rearrangement of (S) 2 chloromethyl-1-ethylpyrrolidine [(S)-1a] to (R)-3-chloro-1-ethylpiperidine [(R) 2a] has been examined at three temperatures in benzene by PMR and polarimetry. The rearrangement was shown to be completely stereospecific and to obey a simple first order rate law. The calculated Ea ΔH3 and ΔS3 were 22 ± 2 (25°), 21 ± 2.5 (25°) and - 10 ± 2 e.u. (0°K) respectively. The effect of solvents having differing dielectric constants was also studied. A transition state 9'a and an ion pair intermediate 3a are suggested for the rearrangement. The stereochemical course of the reactions of (S)-1a, (R)-2a and (S)-2a with hydroxide and methoxide ions have been shown to be 100% stereospecific with an uncertainty of about 1%. The absolute configurations of all optically active reactants and products [(S)- and (R)-4a, (S)-4b (R)- and (S)-5a, (R)-5b, (S,S')-6a, (S,R')-7a and (R,R')-8a] were established by chemical correlations with known compounds or by ORD and chemical inference. The ring opening of both the primary and secondary aziridinium ion positions of 1-azonia-1-ethylbicyclo [3.1.0]hexane [(S)-3a] by nucleophiles proceeds entirely by SN2 processes. The conversion of (R)-1-ethyl-3-hydroxypiperidine [(R)-5a] to (S)-2a. HCl with thionyl chloride in chloroform proceeds by inversion with 4.8% racemization, whereas the thermal rearrangement of (S)-1a to (R)-2a occurs with complete retention of absolute configuration. 相似文献
19.
Compounds MIIMeIVF6 requently undergo phase transitions from the cubic ordered ReO3 to the trigonal LiSbF6 structure when lowering the temperature. In case of a strongly Jahn-Teller unstable cation in the MII position additional phases may occur. Results of powder neutron-diffraction studies on CaSnF6, FeZrF6, and CrZrF6 at different temperatures are reported. The high-temperature phases have the space group Fm3m; the F? ligands are either statistically displaced from the MIIMeIV directions or undergo a strong thermal motion perpendicular to these directions (: 165–180°). The thermal ellipsoids of the CrF bonds are strongly indicative of a dynamical Jahn-Teller effect in addition. In the low-temperature phases of CaSnF6 and FeZrF6 (space group ) the is more distinctly bent (?155–160°). CrZrF6 undergoes two reversible phase transitions, which are determined to occur at 415 ± 5 K (cubic → tetragonal, dynamic to static Jahn-Teller distortion of CrF6 octahedra and 150 ± 10 K (tetragonal → (pseudo)monoclinic). 相似文献
20.
Single crystals of the delafossite-type compound CuAlO2 were grown from Al2O3Cu2O melt by a slow-cooling method from 1200°C. Three types were found in as-grown crystals (single crystals, short-columnar twin crystals with concave angles, and laminar twin crystals). The twinning form is similar to the spinel-type twin. CuAlO2 is rhombohedral, , Z = 3, Dx = 5.12 g/cm3 and Dm = 5.06 g/cm3. The crystal structure of CuAlO2 was analyzed by means of single-crystal X-ray diffraction with a conventional R value = 0.038. The value of the U11 component of the thermal parameter of Cu+ was twice as large as U33. 相似文献