Forms of chemisorbed oxygen on Ag(111): NDDO/MC semiempirical investigation

The atomic and molecular adsorption of oxygen on Ag(111) is calculated by the NDDO/MC semiempirical method. TheAg₃₈ cluster with a rhombic 16-atomic upper (active) face is employed. To model the metallic properties of silver, we used the self-consistent procedure of equalization of the HOMO of the cluster to the experimental Fermi level. Two surface and three subsurface stable sites of atomic adsorption of oxygen are found. According to the results of calculations, molecular adsorption of oxygen is energetically unfavorable but corresponds to the local minimum on the potential energy surface. The role of subsurface oxygen in the activation of the oxygen atom on the surface is discussed.     

Application of the NDDO method to transition metal compounds

The NDDO method has been extended to include elements withd-orbitals. A parametrization for the first-row transition metals is given, which has been worked out to describe structural properties of transition metal complexes. Applications of the method to the Jahn-Teller distortions of tetrachloro complexes are presented. The NDDO results are compared with those from CNDO and INDO calculations. It turns out that the NDDO method seems to be the most sensitive among the ZDO procedures.     

A rapid generalized valence-bond algorithm for semiempirical NDDO calculations

A recently developed algorithm based on the coupled cluster ansatz for the generalized valence-bond perfect-pairing model is adapted for the NDDO class of semiempirical methods. It allows for the calculation of the nondynamic electron correlation and executes as rapidly as the semiempirical molecular orbital method. To assess the interplay of the nondynamic and dynamic electron correlation vs. parameterization, preliminary results are presented for rotation about a double bond, dissociations about single bonds, and the relative stabilities of biradical isomers. © 1995 John Wiley & Sons, Inc.     

CNDO-S2—a semiempirical SCF MO method for transition metal organometallics

A new semiempirical SCF MO procedure available for prediction of the transition metal compounds energy and geometry is developed. The procedure takes an explicit account of the orthogonality of the basis set in the calculation of the core-Hamiltonian elements. A new formula for the resonance integral used in CNDO-S² gives a physically correct treatment of diffuse orbital-localized orbital interaction. The parametrization for atoms H, C, N, O and Ni is presented, with one-center empirical parameters only used. The results of CNDO-S² energy and geometry calculations performed for a number of organic compounds and some nickelorganics are compared with the experimental data. The average absolute errors for the binding energies of organic compounds and nickel complexes are 6.6 kcal/mol and 9.3 kcal/mol respectively.     

A semiempirical model for the two-center repulsion integrals in the NDDO approximation

A self-consistent formalism is proposed for the two-center electron repulsion integrals in the NDDO approximation, based on their expansion in terms of multipole-multipole interactions and free from adjustable parameters.     

Performance of the semiempirical PM3 (tm) method in the geometry optimization of transition metal complexes

The geometries of three different sets of transition metal compounds are optimized with the semiempirical PM3 (tm) method. The systems under test are: (i) products of cyclometallation, like [Pd{C₆H₄[CH(Me)NH₂]}Br(PPh₃)], (ii) molecular dihydrogen complexes, like [W(CO)₃(H₂)(PR₃)₂], and (iii) H‐BR₂ σ complexes of titanium, like TiCp₂(HBcat)₂ (cat = O₂C₆H₄). The results are compared with available X‐ray and neutron diffraction data, as well as with ab initio molecular orbital and density functional theory results published in the literature. The performance of the PM3 (tm) method ranges from excellent in the case of dihydrogen complexes to very poor in the case of H‐BR₂ complexes. © 2000 John Wiley & Sons, Inc. J Comput Chem 21: 562–571, 2000     

Oxygen diffusion through the Ag(111) surface: A quantum chemical study by the NDDO/MC method

Atomic forms of oxygen on the (111) face of metallic silver are studied by the NDDO/MC semiempirical method. The surface (above the octahedral void) and subsurface (within the void) positions of oxygen between the first and second layers of the (111) face are investigated. The potential surface cross section is calculated for the subsurface position of oxygen. A new approach is used to take into account surface relaxation due to reaction with adsorbate. The barrier of atomic oxygen diffusion through the surface is much lower than the banier of its desorption from the surface. The correlation correction to the diffusion and desoption barrier energies is estimated by the double CI (DCIP) method. The greatest correlation effects are obtained in the desorption banier calculation. Translated fromZhumal Stmktunoi Khimii, Vol. 41, No. 2, pp. 248-254, March–April, 2000.     

4,5-diazafluorene-based overcrowded alkene: a new ligand for transition metal complexes

[structure: see text] A new ligand system, where a 4,5-diazafluorene-type chelate and a methoxybenzoxanthene unit are coupled by a double bond has been synthesized and fully characterized including X-ray structure. The synthesis and UV-vis spectra of Ru(II), Os(II), and Re(I) complexes with the above-mentioned ligand are also shown.     

Synthesis of new ligands for transition metal complexes: menthyl- and neomenthyl-cyclopentadienes

Syntheses of (?)-menthylcyclopentadiene (MCp) and (+)-neomenthyl cyclopentadiene (NMCp) from (?)-menthol are described. These chiral ligands have been used to prepare (η⁵-MCp)₂TiCl₂, (η⁵-NMCp)₂, TiCl₂, (η⁵-MCp)₂ZrCl₂, (η⁵-NMCp)₂ZrCl₂, (η⁵-Cp)(η⁵-MCp)TiCl₂ and (η⁵-Cp)(η⁵-NMCp)TiCl₂. The structure and absolute configuration of (η⁵-Cp)(η⁵-MCp)TiCl₂ has been established by X-ray analysis.     

A convenient method for the preparation of barbituric and thiobarbituric acid transition metal complexes

A convenient method for the preparation of barbiturate transition metal complexes: (i) Cr(3+), Mn(2+), Fe(3+), Zn(2+) and Cd(2+) ions with barbituric acid (H(2)L) and (ii) Cr(3+) and Mo(5+) with 2-thiobarbituric acid (H(2)L') was reported and this has enabled seven complexes to be formulated as: [Cr(HL)(2)(OH)(H(2)O)].H(2)O, [Mn(HL)(2)(H(2)O)(2)], [Fe(2)(L)(OH)(3)(H(2)O)(4)].2H(2)O, [Zn(HL)(2)], [Cd(HL)(2)], [Cr(HL')(OH)(2)(H(2)O)].H(2)O and [Mo(HL')(2)]Cl. These new barbiturate complexes were synthesized and characterized by elemental analysis, molar conductivity, magnetic measurements, spectral methods (mid infrared, (1)H NMR, mass, X-ray powder diffraction and UV/vis spectra) and simultaneous thermal analysis (TG and DTG) techniques. The molar conductance measurements proved that, all complexes of barbituric and 2-thiobarbituric acids are non-electrolytes except for [Mo(HL')(2)]Cl. The electronic spectra and magnetic susceptibility measurements were used to infer the structures. The IR spectra of the ligands and their complexes are used to identify the mode of coordination. Kinetic and thermodynamic parameters such as: E, DeltaH, DeltaS and DeltaG are estimated according to the DTG curves. The two ligands and their complexes have been studied for their possible biological antifungal activity.     

A new method for voltammetric determination of the stoichiometry of metal complexes

A new method for voltammetric determination of the composition of metal complexes has been developed. This method can be used in a manner similar to that of molar ratio except that the voltammetric technique is employed instead of the spectroscopic one. The present technique has been applied to the transition metal complexes with some typical uni-, bi-, ter- and sexidentate ligands, and it was found that the compositions determined by this method were in good agreement with those from the spectroscopic technique. A theoretical approach to this method has been presented.     

Divalent transition metal complexes

4-(4-ethoxy-phenylhydrazono)-1-phenyl-3-methyl-1H-pyrazolin-5(4H)-one (5a) (H-EMPhP) as ligand and its Cu(II), Co(II) and Ni(II) complexes 4(a-c) were synthesized and characterized by their thermal and spectral properties. The azocoupling product (H-EMPhP), able of azo-hydrazone tautomerism 5(a-d), act as a bidentate ligand involving in coordination the azogroup nitrogen of its common anion (7) and the oxygen atom that is bound to the pyrazole ring of the mentioned anion (7).     

A fast method of large-scale serial semiempirical calculations of docking complexes

A brief survey of the state of the art in methods of calculations of protein—ligand interaction energies in docking complexes is presented. A new computational technique is proposed that allows one to fundamentally improve the performance of large-scale serial calculations of docking complexes using the AM1/PM3 semiempirical methods. The technique explicitly allows for a specific feature of docking problems, viz., the need for calculating numerous ligand complexes with a specified protein whose noninteracting part remains “frozen” during computations. The interaction energies calculated using the new method differ only slightly from the results of complete AM1 calculations and the performance attained is high enough to solve practical drug design problems. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1759–1764, September, 2008.     

Polyoxometalate tri-supported transition metal complexes containing mixed-valent transition metal ions

Three compounds, [AsMo₈V₆O₄₂][Cu(2,2?-bpy)₂]₂[Cu(2,2?-bpy)]·4H₂O (1), [PMo₈V₆O₄₂][Cu(2,2?-bpy)₂]₂[Cu(2,2?-bpy)]·3H₂O (2) and [PMo₈V₆O₄₂][Cu(2,2?-bpy)₂]₂[Cu(2,2?-bpy)]·3.5H₂O (3), have been synthesized under hydrothermal conditions and characterized by IR, UV–vis, XRD, TG, elemental analysis, and X-ray diffraction analysis. Single-crystal X-ray structure analysis reveals that 1 and 2 are isostructural and isomorphous, whereas 2 and 3 are polymorphs. Polymorphs of 1 have not been synthesized yet. The mixed-valent transition metal ion in 1–3 has been further confirmed by TG analyses. Catalytic properties of 1 and 2 have also been studied.     

Semiempirical NDDO/MC calculations of the excited states of the chromate ion

A new semiempirical method of calculating the excited states of transition metal complexes is developed. This technique uses the configuration interaction and semiempirical NDDO/MC methods to obtain the ground state of a set of Slater type valence spd-orbitals chosen from the optical spectra of transition metals together with the corresponding core integrals. The method is tested in calculations of the electronically excited states of the chromate ion. Good agreement with the experimental energies of vertical transitions and the results of ab initio calculations is achieved.     

A very bulky carboxylic perchlorotriphenylmethyl radical as a novel ligand for transition metal complexes. A new spin frustrated metal system

Reaction of a carboxylic perchlorotriphenylmethyl radical with Cu2(O2CCH3)(4).2H2O using different molar ratios yields two different transition metal complexes with strong intramolecular antiferromagnetic interactions, which in the case of complex 2 follows a butterfly spin frustrated model.     

Manganese‐based transition metal complexes as new catalysts for olefin polymerizations

Three manganese complexes, Mn(acac)₃ (acac = acetylacetonate), Cp₂Mn (Cp = cyclopentadienyl), and Mn(salen)Cl [salen = 1,2‐cyclohexanediamino‐N,N′‐bis(3,5‐dit‐butyl‐salicylidene)], were used for ethylene and propylene polymerizations. These complexes, in combination with an alkylaluminum cocatalyst such as methylaluminoxane (MAO) or diethyl aluminum chloride (AlEt₂Cl), could promote ethylene polymerizations that yielded extremely high molecular weight linear polymers, but were inactive for propylene polymerizations. The counterparts supported on MgCl₂ showed activities even for propylene polymerizations and had remarkably enhanced activities for ethylene polymerizations. In the presence of an electron donor such as ethylbenzoate, the MgCl₂‐supported manganese‐based catalysts yielded a highly isotactic polypropylene with a high molecular weight. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3733–3738, 2001     

Mixed ligand complexes of coumarilic acid/nicotinamide with transition metal complexes

Coumarilate–nicotinamide complexes of Co^II and Zn^II were synthesized and investigated by elemental analysis, magnetic susceptibility, solid state UV–Vis, direct injection probe mass spectra, FTIR spectra, thermoanalytic TG-DTG/DTA, and crystal X-ray diffraction methods. It was obtained that both complex structures contain 2 mol aqua ligands, 2 mol coumarilate (CCA^?) and 2 mol nicotinamide (NA) ligands per formula unit. The CCA^? and NA ligands were bonded to metal cations as monodentate through acidic oxygen and nitrogen of pyridine ring, respectively. Thermal decomposition of each complex starts with dehydration and continue removing of 1 mol NA ligand. The thermal dehydration of the complexes takes place in one or two steps. The decomposition mechanism and thermal stability of the investigated complexes are interpreted in terms of their structures. The final decomposition products are found to be metal oxides.