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Pressure variation of maximumF-band absorption energies in the halides of lithium, sodium and potassium has been investigated employing the extended-ion
approximation for the calculation of theF-electron energy eigenvalues and using values of local compressibility in the neighbourhood of theF-centres which include the effect of vacancy and pressure. The results obtained agree with the experimental results. 相似文献
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The reaction of TaMe(3)Cl(2) with the lithium salt of tetramethylpyrrole (Li-TMP) led to the formation of (eta(5)-TMP)TaMe(3)Cl (1). Reactions of 1 with a series of anionic ligands have been carried out to form products of the formula (eta(5)-TMP)TaMe(3)X, where X = SR, Me, pyrrolyl, or indolyl. Crystals of (eta(5)-TMP)TaMe(3)(indolyl) (5), were isolated in space group P2(1)/c with a = 8.957(2) ?, b = 28.540(6) ?, c = 14.695(3) ?, beta = 99.40(3) degrees, V = 3706.1(14) ?(3), and Z = 8. The structure confirmed the eta(5)-bonding mode of the tetramethylpyrrolyl ligand and the eta(1)-N-coordination mode of the indolyl ligand.The derivatives (eta(5)-TMP)TaMe(3)X showed limited stability, and decomposition products which formed in toluene solutions at room temperature have been identified in some cases. The reaction of (eta(5)-TMP)TaMe(3)(pyrrolyl) with hydrogen (2-3 atm) in benzene-d(6) solution at room temperature was studied. The stoichiometric formation of cyclohexane-d(6) by hydrogenation of an equivalent of solvent was confirmed by (1)H and (13)C NMR and gas chromatographic/mass spectroscopic data. The characteristics and scope of the room temperature arene hydrogenation process are discussed. 相似文献
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Speier G Tyeklár Z Tóth P Speier E Tisza S Rockenbauer A Whalen AM Alkire N Pierpont CG 《Inorganic chemistry》2001,40(22):5653-5659
Bis(pyridine)(9,10-phenanthrenequinone)(9,10-phenanthrenediolato)copper(II), Cu(py)(2)(PhenCat)(PhenBQ), has been prepared by treating copper metal with 9,10-phenanthrenequinone in pyridine solution. In dilute solution, both Cu(py)(2)(PhenCat)(PhenBQ) and the related complex Cu(tmeda)(PhenCat)(PhenBQ) lose PhenBQ to form Cu(II)L(2)(PhenCat), where L(2)= tmeda, 2 py. EPR spectra recorded at temperatures between 300 and 77 K reveal the presence of species with radical and metal localized spins together at equilibrium. Equilibria between Cu(II)L(2)(PhenCat) and Cu(I)L(2)(PhenSQ) redox isomers are solvent dependent, with a shift to higher temperature for polar solvents. Both complexes are oxygen sensitive, reacting with dioxygen to give complexes of diphenic acid. Structural characterization on products obtained with tmeda show that dioxygen insertion across the C-C bond within the chelate ring leads to dimeric products with adjacent Cu(II) ions bridged by diphenate ligands. The addition of O(2) to Cu(tmeda)(PhenCat) in acetonitrile solution at 0 degrees C appears to form a peroxo complex, tentatively identified as Cu(tmeda)(O(2))(PhenQ) on the basis of iodometric titration, as the precursor to the diphenate complex. 相似文献
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Pierpont CG 《Inorganic chemistry》2011,50(20):9766-9772
Ligand noninnocence occurs for complexes composed of redox-active ligands and metals, with frontier orbitals of similar energy. Usually methods of analysis can be used to define the charge distribution, and cases where the metal oxidation state and ligand charge are unclear are unusual. Ligands derived from o-benzoquinones can bond with metals as radical semiquinonates (SQ(?-)) or as catecholates (Cat(2-)). Spectroscopic, magnetic, and structural properties can be used to assess the metal and ligand charges. With the redox activity at both the metal and ligands, reversible multicomponent redox series can be observed using electrochemical methods. Steps in the series may occur at either the ligand or metal, and ligand substituent effects can be used to tune the range of ligand-based redox steps. Complexes that appear as intermediates in a ligand-based redox series may contain both SQ and Cat ligands "bridged" by the metal as mixed-valence complexes. Properties reflect the strength of metal-mediated interligand electronic coupling in the same way that ligand-bridged bimetallics conform to the Robin and Day classification scheme. In this review, we will focus specifically on complexes of first-row transition-metal ions coordinated with three ligands derived from tetrachloro-1,2-benzoquinone (Cl(4)BQ). The redox activity of this ligand overlaps with the potentials of common metal oxidation states, providing examples of metal- and ligand-based redox activity, in some cases, within a single redox series. The strength of the interligand electronic coupling is important in defining the separation between ligand-based couples of a redox series. The complex of ferric iron will be described as an example where coupling is weak, and the steps associated with the Fe(III)(Cl(4)SQ)(3)/[Fe(III)(Cl(4)Cat)(3)](3-) redox series are observed over a narrow range in electrochemical potential. 相似文献
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The general formula for the number of diagrammatic terms occurring in the Tn equation within a particular coupled cluster model is derived. Both the antisymmetrized and Goldstone diagrams are considered. In addition to the full coupled cluster equation approximate approaches are discussed, and for each the general formula for the number of terms is given. Analogous expressions are presented for the number of diagrammatic terms contributing to the elements of the transformed Hamiltonian [Hbar] = e?T HeT . 相似文献
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