Quantum Monte Carlo study of the CO interaction with a dimer model surface for Cr(110)

The chemisorption of CO on a Cr( 110) surface is investigated using the quantum Monte Carlo method in the diffusion Monte Carlo (DMC) variant and a model Cr2CO cluster. The present results are consistent with the earlier ab initio HF study with this model that showed the tilted/ near-parallel orientation as energetically favoured over the perpendicular arrangement. The DMC energy difference between the two orientations is larger (1.9 eV) than that computed in the previous study. The distribution and reorganization of electrons during CO adsorption on the model surface are analysed using the topological electron localization function method that yields electron populations, charge transfer and clear insight on the chemical bonding that occurs with CO adsorption and dissociation on the model surface.

Syntheses and Crystal Structures of Fused Thiophenes: [7]Helicene and Double Helicene, a D-2-Symmetric Dimer of 3,3 '-Bis(dithieno[2,3-b:3 ',2 '-d]thiophene)

The efficient synthesis of (TMS)(2)-[7]helicene (rac-3) and double helicene, a D-2-symmetric dimer of 3,3'-bis(dithieno-[2,3-b:3',2'-d]thiophene) (rac-4) was developed. The crystal structures of 3 and 4 show both strong intermolecular pi-pi interactions and S center dot center dot center dot S interactions. UV/vis spectra reveal that both 3 and 4 show significant pi-electron delocalization.

Methyleneimidazoline Complexes of Iridium, Rhodium, and Palladium from Selective C(sp(3))-H Bond Activation

Palladium, iridium, and rhodium complexes of 2-methyleneimidazolines have been synthesized by selective phosphine-assisted activation of the 2-methyl C-H bonds in 2-methylimidazolium compounds. Metallacycles of various sizes were obtained in the reaction of phosphine-tethered 2-methylimidazolium compounds and [{M(cod)X}(2)] (M = Rh or Ir cod = 1,5-cyclooctadiene: X = alkoxyl or Cl). representative complexes were characterized by X-ray crystallography. The selectivity for aliphatic C(sp(3))H versus aromatic C(sp(2))H activation could be adjusted by means of the steric bulk of the OR ligand, whereby a bulky, OR group favors activation of the 2-methyl C(sp(3))-H bond. Experimental results confirmed that a methyl C-H activation product (a seven-membered iridacycle) is the kinetic product, while the aryl C-H activation product (a six-membered iridacycle) is the thermodynamic product.

Supramolecular architectures, photophysics, and electroluminescence of 1,3,4-oxadiazole-based iridium(III) complexes: From mu-dichloro bridged dimer to mononuclear complexes

One mu-dichloro bridged diiridium complex and three mononuclear iridium(III) complexes based on the 1,3,4-oxadiazole derivatives as cyclometalated ligands and acetylacetonate (acac) or dithiolates O,O'-diethyldithiophosphate (Et(2)dtp) or N,N'-diethyldithiocarbamate (Et(2)dtc) as ancillary ligands have been synthesized and systematically studied by X-ray diffraction analysis. The results reveal that three mononuclear complexes all adopt distorted octahedral coordination geometry around the iridium center by two chelating ligands with cis-C-C and trans-N-N dispositions, which have the same coordination mode as the diiridium dimer. The dinuclear complex crystallizes in the monoclinic system and space group C2/c, whereas three mononuclear iridium complexes are all triclinic system and space group P(1) over bar. In the stacking structure of the dimer, one-dimensional tape-like chains along the b-axis are formed by hydrogen bondings, which are strengthened by pi stacking interactions between phenyl rings of 1,3,4-oxadiazole ligands. Then these chains assemble a three-dimensional alternating peak and valley fused wave-shape structure. In each stacking structure of three mononuclear complexes, two molecules form a dimer by the C-H center dot center dot center dot O hydrogen bondings, and these dimers are connected by pi stacking interactions along the b-axis, constructing a zigzag chain.

Electronic structures of hafnium dimer and trimer by density functional theory

Equilibrium geometries, vibrational frequencies and dissociation energies of hafnium dimer and trimer were studied by density functional methods B3LYP, BLYP, B3PW91, BHLYP, BP86, B3P86, mPW1PW91 and PBE1PBE. The results indicate that singlet is the ground state both for hafnium dimer and for trimer. For hafnium dimer, the calculated bond distance is less sensitive to the methods used. Except at BHLYP level, the calculated vibrational frequency is comparable to the experimental value. For hafnium trimer, equilateral triangle with D-3h symmetry is slightly favored compared with isosceles triangle with C-2v, symmetry except at BHLYP level. This conclusion is in agreement with experiment in which the ground state of Hf-3 is fluxional and low-spin or closed shell is preferred.

Ground state of lutetium dimer by density functional methods

Bond distances, vibrational frequencies and dissociation energies for the ground state of Lu-2 were studied by density functional methods B3LYP, B3PW91, BLYP, BHLYP, BP86, B3P86, MPW1PW91, PBE1PBE and SVWN with CEP-121G and SDD basis sets. Singlet state is predicted to be the most stable. CEP-121G has a better overall performance than SDD. At CEP-121G basis set, all density functional methods used in this study perform well in reproducing the spectroscopic constants.

6,7,8,9-Tetrahydro-5H-pyrido[2,3-b]azepine-5,8-dione: a hydrogen-bonded dimer structure

In the title compound, C9H8N2O2, two crystallographically independent molecules form a dimer structure, in which two N-H center dot center dot center dot N hydrogen bonds generate an intermolecular R-2(2)( 8) ring.

Structure of Cyclic Aryl Thioester Dimer Based on o-Phthaloyl Dichloride and Bis(4-mercaptophenyl) Sulfide

A cyclic aryl thioester dimer was prepared by the reaction of o-phthaloyl dichloride and his (4-mercaptophenyl) sulfide in good yield under pseudo-high dilution conditions via interfacial polycondensation. The structure of the cyclic dimer was confirmed by a combination of MALDI-TOF-MS, FTIR, gel permeation chromatography and MM analyses. The X-ray diffraction study of the single crystal of cyclic thioester dimer obtained from two solutions reveals no severe internal strain on the cyclic structure.

Syntheses and crystal structures of mononuclear rhodium hydrido complexes from the reactions of [Rh(H)(2)(PPh3)(2)(EtOH)(2)]ClO4 with various nitrogen ligands

Reactions of the Rh hydrido complex [Rh(H)(2)(PPh3)(2)(EtOH)(2)]ClO4 (1) With nitrogen ligands such as 2-(4-thiazolyl)benzimidazole (tbz). pyridazine (pdz), imidazole (im) and pyrimidine (pmd) in CH,Cl, afforded Various mononuclear Rh hydrido complexes, [Rh(H)(2)(PPh3)(2)(tbz)]CIO4 (2), [Rh(H)(2)(PPh3)(2)(pdZ)(2)]ClO(4)(.)2CH(2)Cl(2) (3). [Rh(H)Cl(PPh3)(2)(pdz)(2)](ClO4CH2Cl2)-C-. (4). [Rh(H)(2)(PPh3)(2)(im)(2)]ClO(4)(.)2CH(2)Cl(2) (5). [Rh(H)Cl(PPh3)(2)(im)(2)](ClO4CH2Cl2)-C-. (6). [Rh(H)(2)(PPh3)(2)(pmd)(2)](ClO4CH2Cl2)-C-. (7) and the Rh non-hydrido complex [RhCl2(pmd)(4)]ClO4 (8). The Rh complexes 2. 3, 5 and 6 were crystallographically characterized. The formation process was monitored by H-1 NMR and UV-Vis spectra. In all the Rh hydrido complexes, the Rh atom is coordinated by two PPh3. ligands in trans-positions and two nitrogen ligands in the cis-positions. The remaining sites Lire occupied by one or two hydride atoms to form a saturated 18-electron framework in a slightly distorted octahedral geometry. For complex 2 an appreciable inter-molecular pi interaction is observed between planes of tbz and PPh3 ligands, while an intra-molecular hydrogen bonding interaction between C-H and Cl atoms is found in complex 6.

A novel dimer - Heteropolytungstate with a vanadium atom as the centre - Synthesis and structural characterization of (H3O)(4)[VW12O40Na (H2O)(4)](2)

A novel dimer-tungstovanadate, (H3O)(4)[VW12O40Na (H2O)(4)](2), was hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction, IR spectra, TGA-DSC thermal analysis and polarograpy. The yellowish crystal crystallized in the triclinic system, space group P1, a = 1.464 5(3) nm, b = 1.468 6(3) nm, c = 1.411 1(3) nm, alpha = 111.82(2)degrees, beta = 93.17(3)degrees, gamma = 117.47(3)degrees, V = 2.210 6(8) nm(3), Z = 1, D-c = 4.552 g . cm(-3), lambda (Mo K alpha) = 0.071 073 nm, mu = 31.402 mm(-1) F(000) = 2 6481 R = 0.078 0. The title compound consists of two Keggin structure units linked together with two hydrated sodium cations to form a dimer with a porous structure with the pore dimension of 0.766 nm X 0.778 5 nm.