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1.
Despite being implicated as important intermediates, iron(V) compounds have proven very challenging to isolate and characterize. Here, we report the preparation of the iron(V) nitrido complex, [PhB((t)BuIm)(3)Fe(V)≡N]BAr(F24) (PhB((t)BuIm)(3)(-) = phenyltris(3-tert-butylimidazol-2-ylidene)borato, BAr(F24) = B(3,5-(CF(3))(2)C(6)H(3))(4)(-)), by one electron oxidation of the iron(IV) nitrido precursor. Single-crystal x-ray diffraction of the iron(V) complex reveals a four-coordinate metal ion with a terminal nitrido ligand. M??bauer and electron paramagnetic resonance spectroscopic characterization, supported by electronic structure calculations, provide evidence for a d(3) iron(V) metal center in a low spin (S = 1/2) electron configuration. Low-temperature reaction of the iron(V) nitrido complex with water under reducing conditions leads to high yields of ammonia with concomitant formation of an iron(II) species.  相似文献   

2.
The study of magnetic phase transitions in insulating molecular solids provides new insights into mechanisms of magnetic coupling in the solid state and into critical phenomena associated with these transitions. Only a few such materials are known to display cooperative magnetic properties. The use of high-spin molecular components would enhance intermolecular spin-spin interactions and thus a series of chargetransfer (CT) salts have been synthesized that utilize the spin S = 1 molecular cation, [Mn(C(5)(CH(3))(5))(2)](+) (decamethylmanganocenium). The structure and cooperative magnetic behavior of [Mn(C(5)(CH(3))(5))(2)](+)[TCNQ(-) (decamethylmanganocenium 7,7,8,8-tetracyano-p-quinodimethanide) are reported. This salt is a bulk molecular ferromagnet with the highest critical (Curie) temperature (T(c) = 6.2 K) and coercive field (3.6 x 10(3) gauss), yet reported for such a material.  相似文献   

3.
The electron-rich, six-coordinate tris-aryloxide uranium(III) complex [((AdArO)3tacn)U(III)] [where (AdArOH)3tacn = 1,4,7-tris(3-adamantyl-5-tert-butyl-2-hydroxybenzyl)1,4,7-triazacyclononane] reacts rapidly with CO2 to yield [((AdArO)3tacn)U(IV)(CO2)], a complex in which the CO(2) ligand is linearly coordinated to the metal through its oxygen atom (eta1-OCO). The latter complex has been crystallographically and spectroscopically characterized. The inequivalent O-C-O bond lengths [1.122 angstroms (A) for the O-C bond adjacent to uranium and 1.277 A for the other], considered together with magnetization data and electronic and vibrational spectra, support the following bonding model: U(IV)=O=C*-O- <--> U(IV)-OC-O-. In these charge-separated resonance structures, the uranium center is oxidized to uranium(IV) and the CO2 ligand reduced by one electron.  相似文献   

4.
Micromachining allows the formation of micrometer-sized regions of bare gold on the surface of a gold film supporting a self-assembled monolayer (SAM) of alkanethiolate. A second SAM forms on the micromachined surfaces when the entire system-the remaining undisturbed gold-supported SAM and the micromachined features of bare gold-is exposed to a solution of dialkyl disulfide. By preparing an initial hydrophilic SAM from HS(CH(2))(15)COOH, micromachining features into this SAM, and covering these features with a hydrophobic SAM formed from [CH(3)(CH(2))(11)S](2), it is possible to construct micrometer-scale hydrophobic lines in a hydrophilic surface. These lines provide new structures with which to manipulate the shapes of liquid drops.  相似文献   

5.
Organic dianions have been stabilized by (M(C(5)(CH(3))(5))(2))(+), where M is iron or cobalt. This has allowed the structural and spectroscopic characterization of these dianions. The structure of (M(C(5)(CH(3))(5))(2))(2)(+) (DDQ)(2-), where DDQ is 2,3-dichloro-5,6-dicyanobenzoquinone, has been determined by x-ray crystallography. The structure of (DDQ)(2-)is consistent with ab initio molecular orbital calculations that suggest a localizd as opposed to a delocalized (aromatic) ring structure.  相似文献   

6.
Cleavage of the relatively inert dinitrogen (N(2)) molecule, with its extremely strong N identical withN triple bond, has represented a major challenge to the development of N(2) chemistry. This report describes the reductive cleavage of N(2) to two nitrido (N(3-)) ligands in its reaction with Mo(NRAr)(3), where R is C(CD(3))(2)CH(3) and Ar is 3,5-C(6)H(3)(CH(3))(2'), a synthetic three-coordinate molybdenum(III) complex of known structure. The formation of an intermediate complex was observed spectroscopically, and its conversion (with N identical withN bond cleavage) to the nitrido molybdenum(VI) product N identical withMo(NRAr)(3) followed first-order kinetics at 30 degrees C. It is proposed that the cleavage reaction proceeds by way of an intermediate complex in which N(2) bridges two molybdenum centers.  相似文献   

7.
Very complicated inorganic solids can be self-assembled from structurally simple precursors as illustrated by the hydrothermal synthesis of the vanadium phosphate, [(CH(3))(2)NH(2)]K(4)[V(10)O(10)(H(2)O)(2)(OH)(4)(PO(4))(7)].4H(2)O, 1, which contains chiral double helices formed from interpenetrating spirals of vanadium oxo pentamers bonded together by P(5+). These double helices are in turn intertwined with each other in a manner that generates unusual tunnels and cavities that are filled with (CH(3))(2)NH(2)(+) and K(+) cations, respectively. The unit cell contents of dark blue phosphate 1, which crystallizes in the enantiomorphic space group P4(3) with lattice constants a = 12.130 and c = 30.555 angstroms, are chiral; only one enantiomorph is present in a given crystal. Magnetization measurements show that 1 is paramagnetic with ten unpaired electrons per formula unit at higher temperatures and that antiferromagnetic interactions develop at lower temperatures.  相似文献   

8.
Single crystals of the layered organic-inorganic perovskites, [NH(2)C(I=NH(2)](2)(CH(3)NH(3))m SnmI3m+2, were prepared by an aqueous solution growth technique. In contrast to the recently discovered family, (C(4)H(9)NH(3))(2)(CH(3)NH(3))n-1SnnI3n+1, which consists of (100)-terminated perovskite layers, structure determination reveals an unusual structural class with sets of m <110>-oriented CH(3)NH(3)SnI(3) perovskite sheets separated by iodoformamidinium cations. Whereas the m = 2 compound is semiconducting with a band gap of 0.33 +/- 0.05 electron volt, increasing m leads to more metallic character. The ability to control perovskite sheet orientation through the choice of organic cation demonstrates the flexibility provided by organic-inorganic perovskites and adds an important handle for tailoring and understanding lower dimensional transport in layered perovskites.  相似文献   

9.
The system IrX(CO)[P(C(6)H(5))(3)](2) in benzene solution adds mo lecular oxygen reversibly if X is chlorine and irreversibly if X is iodine. The crystal structure of the complex IrIO(2)(CO)[P(C(6)H(5))(3)](2) * CH(2)Cl(2) is reported here and compared with a previous study of the structure of IrClO(2)(CO)[P(C(6)H(5))(3)](2). The O-O bond length is 1.47 +/- 0.02 angstroms in the irreversibly oxygenated iodo-compound and 1.30 +/- 0.03 angstroms in the reversibly oxygenated chloro compound.  相似文献   

10.
Conjugated organic compounds with 3-phenyl-5-isoxazolone or N,N'-diethylthiobarbituric acid acceptors have large first molecular hyperpolarizabilities (beta) in comparison with compounds with 4-nitrophenyl acceptors. For example, julolidinyl-(CH=CH)(3)-CH=N,N'- diethylthiobarbituric acid, which has 12 atoms between the donor and acceptor, has a beta(0) of 911 x 10(-30) electrostatic units, whereas (CH(3))(2)NC(6)H(4),-(CH=CH)(4)-C(6)H(4)NO(2), with 16 atoms between its donor and acceptor, has a beta(0) of 133 x 10(-30) electrostatic units. The design strategies demonstrated here have resulted in chromophores that when incorporated into poled-polymer electrooptic modulators exhibited significant enhancements in electrooptic coefficients relative to polymers containing the commonly used dye Disperse Red-1. Poled polymer devices based on these or related chromophores may ultimately lead to high-speed electrooptic switching elements with low drive-power requirements, suitable for telecommunications applications.  相似文献   

11.
Uranium nitrides offer potential as future nuclear fuels and as probes of metal ligand multiple bonding involving the f-block actinide metals. However, few molecular examples are available for study owing to the difficulties in synthesis. Recent advances in organoactinide chemistry have provided a route to uranium nitride complexes that expands the options for developing UN chemistry. Several 24-membered uranium nitrogen rings, (UNUN3)4, have been synthesized by reduction of sodium azide with organometallic metallocene derivatives, [(C5Me4R)2U][(mu-Ph)2BPh2] (R = Me, H; Me = methyl, Ph = phenyl). The nanometer-sized rings contain unusual UNU nitride linkages that have short U-N distances within the double-bond range.  相似文献   

12.
The mineral ammonioborite is monoclinic with unit cell dimensions (in angstroms): a = 25.27, b = 9.65, and c = 11.56; beta = 94 degrees 17', and the space group is C 2/c. Analysis of the crystal structure revealed the crystallo-chemical formula (NH(4))(3)B(15)O(20)(OH)(8).4H(2)O, with four such formula units in the unit cell. The basic structural unit is the double ring consisting of one BO(4) tetrahedron and four BO(3) triangles: in ammonioborite three of these units are connected to give trimeric ions [B(15)O(20)(OH)(8)](3-).  相似文献   

13.
Magnetic anisotropy measurements on single crystals of a series of paramagnetic 8-coordinate lanthanide shift reagent adducts of the type Ln[(CH(3))(3)CCOCHCOC(CH(3))(3)(4-CH(3)C(5)H(1)N)(2) have been made for the following lanthanides: praseodymium, neodymium, samarium, europium, terbium, dysprosium, holmium, erbium, thulium, and ytterbium. The susceptibility tensors are highly anisotropic and nonaxial. Dipolar nuclear magnetic resonance shifts evaluated from the solid-state date are in satisfactory agreement with the solution results.  相似文献   

14.
Direct catalytic hydration of terminal alkenes to primary alcohols would be an inexpensive route to industrially useful alcohols and a convenient synthetic route for the synthesis of terminal alcohols in general. The reaction between trans- PtHCl(PMe(3))(2) (where Me = CH(3)) and sodium hydroxide in a one-to-one mixture of water and 1-hexene yields a species that, at 60 degrees C and in the presence of the phasetransfer catalyst benzyltriethylammonium chloride, catalyzes selective hydration of 1-hexene to n-hexanol at a rate of 6.9 +/- 0.2 turnovers per hour. Hydration of 1-dodecene to n-dodecanol occurs at a rate of 8.3 +/- 0.4 turnovers per hour at 100 degrees C. Deuterium labeling experiments with trans-PtDCl(PMe(3))(2) show that hydration involves reductive elimination of a C-H bond. At low hydroxide concentrations (<8 equivalents), hydration of the water-soluble olefin 3-butene-1-ol to 1,4-butanediol exhibited a first-order dependence on hydroxide concentration for loss of catalytic activity. This suggests that hydroxide attacks the coordinated alkene slowly. At high hydroxide concentrations, the rate of catalysis was hydroxide-independent and first order in alkene. Substitution of coordinated water (k(1) = 9.3 +/- 0.5 x 10(-3) liters per mol per second) appears to be limitng under these conditions.  相似文献   

15.
The rate constant of the electron-transfer reaction between a gold electrode and an electroactive ferrocene group has been measured at a structurally well-defined metal-electrolyte interface at temperatures from 1 degrees to 47 degrees C and reaction free energies from -1.0 to +0.8 electron volts (eV). The ferrocene group was positioned a fixed distance from the gold surface by the self-assembly of a mixed thiol monolayer of (eta(5)C(5)H(5))Fe(eta(5)C(5)H(4))CO(2)(CH(2))(16)SH and CH(3)(CH(2))(15)SH. Rate constants from 1 per second (s(-1)) to 2 x 10(4) s(-1) in 1 molar HClO(4) are reasonably fit with a reorganization energy of 0.85 eV and a prefactor for electron tunneling of 7 x 10(4) s(-1) eV(-1). Such self-assembled monolayers can be used to systematically probe the dependence of electron-transfer rates on distance, medium, and spacer structure, and to provide an empirical basis for the construction of interfacial devices such as sensors and transducers that utilize macroscopically directional electron-transfer reactions.  相似文献   

16.
Polychalcogenide compounds with open polymeric frameworks are rare, and they represent a class of compounds in which microporosity might be achieved. Microporous frameworks that are not oxide-based are now attracting interest because of the combination of catalytic and electronic properties they may simultaneously possess. Three new compounds that may be forerunners to such materials have been discovered and are reported here. The reaction of gallium (Ga), indium (In), and thallium (TI) metal with (Ph(4)P)(2)Se(5) (Ph, phenyl) and an excess of elemental selenium (Se) in a sealed, evacuated Pyrex tube at 200 degrees C yielded small red crystals of (Ph(4)P)[Ga(Se(6))(2)] (I), (Ph(4)P)[In(Se(6))(2)] (II), and (Ph(4)P)[TI(Se(6))(2)] (III), respectively. The [M(Se(6))(2)](-) (M = Ga, In, TI) ions form a two-dimensional, open framework filled with Ph(4)P(+) ions. The [M(Se(6))(2)](n)(n-) structure consists of tetrahedral M(3+) centers and bridging Se(6)(2-) ligands, leading to an extended structure in two dimensions. These layers stack perfectly one on top of the other giving rise to one-dimensional channels running down the c axis that are filled with Ph(4)P(+) cations. These cations are situated in the layers, as opposed to between the layers, and the whole structure can be viewed as a template. Compound II shows remarkable thermal stability and melts congruently at 242 degrees C. Upon cooling to room temperature it gives a glassy phase that recrystallizes upon subsequent heating to 160 degrees C.  相似文献   

17.
The orthorhombic crystal structures of shattuckite, Cu(5)( SiO(3))(4)(OH)(2) and planchétite, Cu(8)(Si(4)0(11))(2)(OH)(4) H(2)O, have been solved. Shattuckite contains silicate chains similar to pyroxene in a complex association with copper atoms, while the closely related planchéite contains silicate chains similar to amphibole.  相似文献   

18.
Merlino S 《Science (New York, N.Y.)》1969,166(3911):1399-1401
As judged by crystal structure analysis, the crystallochemical formula of tuhualite is (Na,K)(2)(VI) (Fe(+3))(2)(VI) (Fe(+2))(2)(VI) Si(12)O(30) . H(2)O, with four such formulas in the unit cell. The structure is characterized by six-repeat double chains of silicon tetrahedrons and chains of edge-sharing, alternating iron tetrahedrons and octahedrons. Chains of each kind are connected by corner sharing to four chains of the other type. The iron cations appear to be anomalously ordered with Fe(+2) in tetrahedral and Fe(+3) in octahedral sites.  相似文献   

19.
A new mineral, stanfieldite, Ca(4)(Mg,Fe)(5)(PO(4))(6), has been found in the Estherville mesosiderite and several pallasites: Santa Rosalia, Albin, Finmarken, Imilac, Mount Vernon, and Newport. The atom ratio Mg:Fe of this mineral varies from 1.5 in Estherville to a constant ratio of about 15 in the pallasites. X-ray, optical, and chemical data for the mineral resemble those for the only intermediate compound in the system Mg(3)(PO(4))(2)-Ca(3)(PO(4))(2).  相似文献   

20.
The compound [Fe(tvp)(2)(NCS)(2)] . CH(3)OH, where tvp is 1,2-di-(4-pyridyl)-ethylene, has been synthesized and characterized by x-ray single-crystal diffraction. It consists of two perpendicular, two-dimensional networks organized in parallel stacks of sheets made up of edge-shared [Fe(II)](4) rhombuses. The fully interlocked networks define large square channels in the [001] direction. Variable-temperature magnetic susceptibility measurements and M?ssbauer studies reveal that this compound shows low-spin to high-spin crossover behavior in the temperature range from 100 to 250 kelvin. The combined structural and magnetic characterization of this kind of compound is fundamental for the interpretation of the mechanism leading to the spin crossover, which is important in the development of electronic devices such as molecular switches.  相似文献   

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