Cl Bond Lengths Research Articles

Crystal structure of [1,3-bis-(2,4,6-tri-methyl-phen-yl)imidazolidin-2-yl-idene]di-chlorido-(2-{[(2-methoxyeth-yl)(meth-yl)amino]-meth-yl}benzyl-idene)ruth-en-ium.

The title compound, [RuCl2(C33H43N3O)], is an example of a new generation of N,N-dialkyl ruthenium catalysts with an N-Ru coordination bond as part of a six-membered chelate ring. The Ru atom has an Addison τ parameter of 0.244, which indicates a geometry inter-mediate between square-based pyramidal and trigonal-bipyramidal. The complex shows the usual trans arrangement of the two chlorides, with Ru-Cl bond lengths of 2.3515 (8) and 2.379 (7) Å, and a Cl-Ru-Cl angle of 158.02 (3)°. One of the chlorine atoms and the atoms of the 2-meth-oxy-N-methyl-N-[(2-methyl-phen-yl)meth-yl]ethane-1-amine group of the title complex display disorder over two positions in a 0.889 (2): 0.111 (2) ratio.

Synthesis of catena-Poly[[di-aqua(2,2′-bipyridine)copper(II)]-μ2-sulfato-κ2O:O'] 1D coordination polymer and [di-chloro(2,2′-bipyridine)copper(II)] complex, redetermination of their crystal structures

The title compounds [Cu(bpy)(H2O)2(SO4)]n (1) and [Cu(bpy)Cl2] (2) were successfully synthesized, and their crystal structures were redetermined as some corrections were needed. The Cu(II) centers in 1 are coordinated in elongated octahedral geometry by the two nitrogen atoms of a bpy ligand and four oxygen atoms belonging to aqua molecules and sulfato ligands, forming a polymeric chain by bridging the sulfato ligands. The Cu(II) center in 2 is coordinated by the two chloride ions and the two nitrogen atoms of the bipyridine ligand, forming a distorted square planar geometry. The [Cu(bpy)(H2O)2(SO4)]n complex crystallizes in the monoclinic crystal system with space group C2/c. The unit cell parameters were determined to be a = 15.154(3) Å, b = 12.477(3) Å, c = 7.0158(14) Å, α = 90°, β = 105.873(12)°, γ = 90°, V = 1276.0(5) Å3, Z = 4. The Cu–N, Cu–O(aqua) and Cu–O(sulfate) bond lengths are 2.000(3) Å, 1.978(2) Å and 2.464(2) Å, respectively. The [Cu(bpy)Cl2] complex crystallizes in the monoclinic crystal system with space group I2/a. The unit cell parameters were determined to be a = 7.306(2) Å, b = 9.016(2) Å, c = 15.879(6) Å, α = 90°, β = 92.141(15)°, γ = 90°, V = 1045.2(5) Å3, Z = 4. The Cu–N and Cu–Cl bond lengths are 2.031(5) Å and 2.2662(17) Å, respectively.

Crystal structure, mechanical, electronic, optical and thermoelectric characteristics of Cs2MCl6 (M = Se, Sn, Te and Ti) cubic double perovskites

The crystal structure, mechanical, electronic, optical and thermoelectric characteristics of Cs2MCl6 (M = Se, Sn, Te and Ti) cubic double perovskites are studied within GGA, GGA-mBJ and EV-GGA functionals. The M − Cl bond lengths are shorter and especially in Cs2TiCl6 double perovskite, which reflects the strong interaction between M and Cl atoms and this is correlated with its better chemical stability. The negativity of formation energy and Helmholtz free energy and no imaginary phonon modes throughout the Brillouin zone confirm the thermal, thermodynamic and dynamical stability of these double perovskites. Semiconductors Cs2MCl6 (M = Se, Sn, Te and Ti) double perovskites with flat conduction and valence bands, and an indirect band gap are p-type carriers. A high Seebeck coefficient, adequate ZT values ​​and non-toxicity make these compounds attractive for thermoelectric applications at high temperature and spintronic technology. The empty first conduction band corresponds to their band gap, and the transition occurs from Cl-p to (Se-p, Sn-p, Te-p and Ti-d). The high static dielectric constant and the intense peak of the real part in the ultraviolet energy range favor less the recombination rate of charge carriers and their use in optoelectronic devices. The indirect band gap, high absorption in ultraviolet energy, high static refractive index make these cubic double perovskites as ideal materials for solar cell applications.

Degradation pathways of atrazine by electrochemical oxidation at different current densities: Identifications from compound-specific isotope analysis and DFT calculation

Current density was the key factor that impacted pollutant degradation by electrochemical oxidation, and reaction contributions at various current densities were non-negligible for the cost-effective treatments of organic pollutants. This research introduced compound specific isotope analysis (CSIA) into atrazine (ATZ) degradation by boron doped diamond (BDD) with current density of 2.5–20 mA/cm2, in order to provide “in-situ” and “fingerprint” analysis of reaction contributions with changed current densities. As results, the increased current density displayed a positive impact on ATZ removal. The ɅC/H values (correlations of Δδ13C and Δδ2H) were 24.58, 9.18 and 8.74 when current densities were 20, 4, and 2.5 mA/cm2, with ·OH contribution of 93.5%, 77.2% and 80.35%, respectively. While DET process favored lower current density with contribution rates up to ∼20%. What's more interesting, though the carbon and hydrogen isotope enrichment factors (εC and εH) were fluctuate, the ɅC/H linearly increased accompanied with applied current densities. Therefore, increasing current density was effective due to the larger ·OH contribution even though side reactions may occur. DFT calculations proved the increase of C–Cl bond length and the delocalization of Cl atom, confirming dechlorination reaction mainly occurred in the direct electron transfer process. While ·OH radical mainly attack the C–N bond on the side chain, which was more benefit to the fast decomposition of ATZ molecule and intermediates. It was forceful to discuss pollutant degradation mechanism by combining CSIA and DFT calculations. Target bond cleavage (i.e., dehalogenation reaction) can be conducted by changing reaction conditions like current density due to the significantly different isotope fractionation and bond cleavage.

The copper(II) coordination chemistry of alkyl substituted bispyrazole pyridine ligands: Structure and spectral properties

Tridentate, planar nitrogen containing ligands based on pyridine and pyrazoles were synthesized by the reaction of 2,6-dibromopyridine with the sodium salts of 3,5-dimethylpyrazole and 3,5-diisopropylpyrazole to yield 2,6-bis(3,5-dimethyl-N-pyrazolyl)pyridine (L0py) and 2,6-bis(3,5-diisopropyl-N-pyrazolyl)pyridine (L1py), respectively. The conformation of the pyrazole rings in the solid-state structures of both L0py and L1py were anti due to relatively low repulsion between the alkyl substituents. Both copper(II) chlorido complexes [CuCl2(L0py)] and [CuCl2(L1py)] were five-coordinate with solid-state structures best described as distorted square-pyramidal geometry involving N3Cl2 donor sets. The ν(Cu–Cl) energies and Cu–Cl bond lengths were clearly different due to the different donating properties of the two ligands. By comparison, the structure of copper(II) trifluoromethanesulfonato complex [Cu(OTf)2(H2O)(L1py)] was six-coordinate with highly distorted octahedral geometry involving an N3O3 donor set. The solution UV–Vis spectra of [CuCl2(L0py)], [CuCl2(L1py)], and [Cu(OTf)2(H2O)(L1py)] revealed π-π* transition bands red-shifted by ∼30 nm on complexation. The d-d transition bands of all three copper(II) complexes were observed at almost the same energy of ∼750 nm, while the corresponding solid-state UV–Vis spectra exhibited absorptions at ∼1010 nm and 674 nm due to differences in coordination geometry. These structural changes in the solution-state were supported by results from EPR spectroscopy.

Crystal structure of chlorido-[diphen-yl(thio-phen-2-yl)phosphine-κP]gold(I).

The crystal structure of the title compound, [AuCl(C16H13PS)], is reported. The mol-ecular structure features a nearly linear arrangement of the chloride and phosphino ligands around the gold(I) center, with a P-Au-Cl bond angle of 179.42 (9)°. The Au-P and Au-Cl bond lengths are 2.226 (2) and 2.287 (2) Å, respectively. The geometry of the groups bonded to the phospho-rus atom of the ligand is a slightly distorted tetra-hedron. The phenyl and thienyl rings of the ligand are extensively disordered, with the thienyl refined over all three possible positions on the phospho-rus atom. The relative occupancy ratio between these positions was found to be 0.406 (3):0.406 (2):0.188 (2). One of the major thienyl ring positions with the relative occupancy of 0.406 was modeled as two rotational isomers around the C-P bond with a relative occupancy ratio of 0.278 (3):0.128 (3). Inter-molecular C-H⋯π inter-actions present in the crystal lattice link mol-ecules of the title compound together to form a complex three-dimensional network.

Bulky Thiolate-Protected Silver Nanocluster Ag 213 (Adm-S) 44 Cl 33 with Excellent Electrocatalytic Performance toward Oxygen Reduction

Bulky Thiolate-Protected Silver Nanocluster Ag ₂₁₃ (Adm-S) ₄₄ Cl ₃₃ with Excellent Electrocatalytic Performance toward Oxygen Reduction

Дихлородицианоаураты органилтрифенилфосфония [Ph3PR][Au(CN)2Cl2] (R = n-Pr, i-Bu, n-Hp): синтез и строение

The interaction of potassium dichlorodicyanoaurate with n-propyl-, i-butyl- and n-heptyltriphenylphosphonium bromides in water followed by the recrystallization from acetoni-trile leads to the dichlorodicyanoaurate complexes [Ph3P(n-Pr)][Au(CN)2Cl2] (1), [Ph3P(i Bu)][Au(CN)2Cl2] (2), and [Ph3P(n-Hp)][Au(CN)2Cl2] (3). Compounds 1 and 2 have been identified by the IR spectroscopy; structure of compound 3 has been determined by the X-ray diffraction analysis. According to the X-ray data, complex 3 consists of n-heptyltriphenylphosphonium cation and two types of crystallographically independent centrosymmetric square-planar dichlorodicyanoaurate anions. The phosphorus atom in the cation has a slightly distorted tetrahedral coordination with the CPC bond angles within the interval 108.3(5)–110.5(5)°; the P–C distances are 1.801(10)–1.832(10) Å. The square-planar coordination of the gold atoms in centrosymmetric anions [Au(CN)2Cl2] is almost undistorted: the CAuC and ClAuCl trans-angles equal 180, the CAuCl cis-angles vary in a narrow range 74.5(9)–105.5(9). The Au–Cl bond lengths in anions do not exceed the sum of the covalent radii of the gold and chlorine atoms and equal 2.406(3), 2.388(3) Å; the Au–C bond lengths are 2.021(14), 2.037(13); they are close to the sum of the covalent radii of the gold and carbon atoms. The structural organization in crystals 3 is caused by the H∙∙∙N≡C (2.55–2.63 Å) and С–H∙∙∙Cl–Au (2.87 Å) hydrogen bonds. Moreover, the structure contains the additional С–H∙∙∙π(Ph) contacts with the distances from the hydrogen atom to the plane of the benzene ring that are equal to 2.80 Å. Complete tables of atomic coordinates, bond lengths, and valence angles are deposited in the Cambridge structural data Bank (No. 2094701 for 3; deposit@ccdc.cam.ac.uk; http://www.ccdc.cam.ac.uk).

Halogen Bonding in the Complexes of Brominated Electrophiles with Chloride Anions: From a Weak Supramolecular Interaction to a Covalent Br–Cl Bond

The wide-range variation of the strength of halogen bonds (XB) not only facilitates a variety of applications of this interaction, but it also allows examining the relation (and interconversion) between supramolecular and covalent bonding. Herein, the Br…Cl halogen bonding in a series of complexes of bromosubstituted electrophiles (R-Br) with chloride anions were examined via X-ray crystallographic and computational methods. Six co-crystals showing such bonding were prepared by evaporation of solutions of R-Br and tetra-n-propylammonium chloride or using Cl− anions released in the nucleophilic reaction of 1,4-diazabicyclo[2.2.2]octane with dichloromethane in the presence of R-Br. The co-crystal comprised networks formed by 3:3 or 2:2 halogen bonding between R-Br and Cl−, with the XB lengths varying from 3.0 Å to 3.25 Å. Analysis of the crystallographic database revealed examples of associations with substantially longer and shorter Br…Cl separations. DFT computations of an extended series of R–Br…Cl− complexes confirmed that the judicious choice of brominated electrophile allows varying halogen Br…Cl bond strength and length gradually from the values common for the weak intermolecular complexes to that approaching a fully developed covalent bond. This continuity of halogen bond strength in the experimental (solid-state) and calculated associations indicates a fundamental link between the covalent and supramolecular bonding.

Crystal structure and spectroscopic properties of aqua-dichlorido-{1,1'-[(pyridine-2,6-diyl-κN)bis(methyl-ene)]bis-(4-butyl-4,5-di-hydro-1H-1,2,4-triazole-5-thione-κN 2)}cobalt(II).

The structure of the title compound, [CoCl2(C19H27N7S2)(H2O)], at 173 K has monoclinic (C2/c) symmetry. We report here the synthesis, single-crystal structure, electrospray mass spectrum and NMR spectroscopy of a new six-coordinate cobalt(II) pincer complex. The pincer ligand, in this complex, which is novel, coordinates via three nitro-gen atoms (two triazole and one pyridine). The ligand is ambidentate and can coordinate via three nitro-gen atoms or two sulfur and one nitro-gen atoms. The cobalt(II) metal center has pseudo-octa-hedral geometry and based on the single-crystal structure, the pincer ligand coordinates in a meridional fashion with the metal and adjacent six-membered ring ligands all in a similar plane and forming two slightly distorted boat configurations. The other two coordinated monodentate ligands are one water mol-ecule and two chloride ions with four cobalt(II) complexes in the unit cell. The asymmetric unit of the complex is comprised of half the pyridine ring and water mol-ecule with the CoII atom at the center of the pincer situated about a twofold axis. The Co-N, Co-O, and Co-Cl bond lengths are consistent with single bonds. In the crystal, the complex forms a three-centre bifurcated weak hydrogen-bonding inter-action with a chlorine ion, forming one inter-molecular inter-action with the pincer group and a water mol-ecule and a second intra-molecular inter-action with a C-H group within the pincer group. Crystal packing is also highlighted with C 2 2(6)>a<a infinite chains forming along [001] supported by R 2 2(8)>a>a ring motifs, forming a three-dimensional supra-molecular network structure. While some stacking of the pyridine rings in the unit cell is observed, there are no relevant π-π inter-actions in the crystal packing. The 1H and 13C{1H} NMR spectra of the complex are consistent with a plane of symmetry being present. The electrospray mass spectrum, which was collected in positive ion mode, showed the loss of one water mol-ecule and one chloride ligand from the complex. In the future, we plan to screen this cobalt(II) complex for electrocatalysis reactivity.

An ab initio study of some hydrogen-bonded complexes of chloroform and bromoform: red-shifted or blue-shifted hydrogen bonds?

The properties of the hydrogen-bonded complexes of chloroform and bromoform with ammonia, water, hydrogen fluoride, phosphine, hydrogen sulphide and hydrogen chloride were studied by means of ab initio calculations. The properties of interest were the molecular structures, the interaction energies, the vibrational spectra and the nature of the orbital interactions involved in the formation of the complexes. Of particular interest was the determination of whether the various interactions exhibited red-shifted or blue-shifted hydrogen bond behaviour. The complexes optimized in three distinct structural models, singly bonded, cyclic and cage. The interaction energies, in the main, varied systematically with changes of the haloform and of the partner molecules. Changes of the CH or YH (Y = N, O, F, P, S and Cl) bond lengths correlated in most cases with the interaction energies, subject to some inconsistencies, with opposite behaviour being shown by the two sets. Similarly, the CH and YH stretching wavenumber shifts also displayed a dependence on the interaction energies, tracking with the bond length changes. Based on the diagnostic utility of these structural and spectroscopic properties, the complexes were found to be almost exclusively red-shifted, for binding through both the CH and YH groups. The orbital interactions responsible for the stability of the complexes were determined to be donation from a Y atom lone pair orbital of the partner molecule to a CH σ antibonding orbital and from a X lone pair orbital (X = Cl and Br) of the haloform to a YH σ antibonding orbital.

Magnetic Properties of a New Hexahalorhenate(IV) Compound and Structural Comparison with Its Hexahaloplatinate(IV) Analog

Two mononuclear complexes of formula (Et3BzN)2[ReCl6] (1) and (Et3BzN)2[PtCl6] (2) (Et3BzN+ = triethylbenzylammonium cation) have been synthesized in good yield (70 and 75 %, respectively) and structurally characterized. From a structural point of view, they both crystallized in the monoclinic centrosymmetric P21/n space group and the two molecular structures are almost perfectly superimposable, with only minor differences in the M–Cl bond lengths. Solid‐state direct‐current (dc) magnetic susceptibility analysis in the temperature range 1.9–300 K for 1 reveal the occurrence of magnetically isolated rhenium(IV) ions with a significant zero‐field splitting (zfs), D = +6.7 cm–1 (2D being the energy gap between the MS = ±3/2 and MS = ±1/2 Kramers doublets). DFT, CASSCF and CASSCF/NEVPT2 theoretical calculations were carried out on the experimental geometry of the complex [ReCl6]2– in 1 to substantiate the parameters defining the zfs tensor. Alternating current (ac) magnetic susceptibility measurements of 1 in the temperature 2.0–10 K show incipient frequency–dependence of the out‐of‐phase signals below 3.0 K under non‐zero applied dc fields supporting a field–dependent Single Ion Single Molecule Magnet (SISMM) behaviour of this rhenium(IV) derivative.

High CO2 absorption capacity of metal-based ionic liquids: A molecular dynamics study

The absorption of CO2 is of importance in carbon capture, utilization, and storage technology for greenhouse gas control. In the present work, we clarified the mechanism of how metal-based ionic liquids (MBILs), Bmim[XCln]m (X is the metal atom), enhance the CO2 absorption capacity of ILs via performing molecular dynamics simulations. The sparse hydrogen bond interaction network constructed by CO2 and MBILs was identified through the radial distribution function and interaction energy of CO2-ion pairs, which increase the absorption capacity of CO2 in MBILs. Then, the dynamical properties including residence time and self-diffusion coefficient confirmed that MBILs could also promote the diffusion process of CO2 in ILs. That's to say, the MBILs can enhance the CO2 absorption capacity and the diffusive ability simultaneously. Based on the analysis of structural, energetic and dynamical properties, the CO2 absorption capacity of MBILs increases in the order Cl− → [ZnCl4]2−→ [CuCl4]2−→ [CrCl4]− → [FeCl4]−, revealing the fact that the short metal–Cl bond length and small anion volume could facilitate the performance of CO2 absorbing process. These findings show that the metal–Cl bond length and effective volume of the anion can be the effective factors to regulate the CO2 absorption process, which can also shed light on the rational molecular design of MBILs for CO2 capture and other key chemical engineering processes, such as IL-based gas sensors, nano-electrical devices and so on.

Examination of the Magneto-Structural Effects of Hangman Groups on Ferric Porphyrins by EPR.

Ferric hangman porphyrins are bioinspired models for haem hydroperoxidase enzymes featuring an acid/base group in close vicinity to the metal center, which results in improved catalytic activity for reactions requiring O-O bond activation. These functional biomimics are examined herein with a combination of EPR techniques to determine the effects of the hanging group on the electronics of the ferric center. These results are compared to those for ferric octaethylporphyrin chloride [Fe(OEP)Cl], tetramesitylporphyrin chloride [Fe(TMP)Cl], and the pentafluorophenyl derivative [Fe(TPFPP)Cl], which were also examined herein to study the electronic effects of various substituents. Frequency-domain Fourier-transform THz-EPR combined with field domain EPR in a broad frequency range from 9.5 to 629 GHz allowed the determination of zero-field splitting parameters, revealing minor rhombicity E/D and D values in a narrow range of 6.24(8) to 6.85(5) cm-1. Thus, the hangman porphyrins display D values in the expected range for ferric porphyrin chlorides, though D appears to be correlated with the Fe-Cl bond length. Extrapolating this trend to the ferric hangman porphyrin chlorides, for which no crystal structure has been reported, indicates a slightly elongated Fe-Cl bond length compared to the non-hangman equivalent.

Chlorates and perchlorates as potential high-energy materials: chlorate- and perchlorate-substituted methanes

The structures and properties of thirty-three of the thirty-four possible chlorato-Cl-, chlorato-O- and perchlorato-derivatives of methane have been computed using the range-separated hybrid generalized gradient approximation density functional method ωB97X-D with the 6-311+G(2d,p) basis set. These results indicate that the chlorato-O-substituent confers more stability to a molecule than does the chlorato-Cl-substituent; the perchlorato-substituent is approximately intermediate in this regard when decomposition energies are calculated. The C–Cl bond lengths in the chlorato-Cl-substituents generally elongate and the C–O distances in the chlorato-O- and perchlorato-substituents tend to shorten as the number of chlorate/perchlorate substituents increases. In addition, as the C–O bond shortens, the CO–Cl bond lengthens. The calculated Mulliken and Löwdin bond orders for these bonds exhibit the opposite of the trends exhibited by the bond lengths, as expected: As the bond lengthens, the bond order decreases, and vice versa. The single molecule that could not be optimized as a stable methane derivative, (chlorato-Cl-)tris(chlorato-O-)methane, rearranged during all optimization attempts to an isomer of the neutral Cl2O5 molecule and a hitherto unknown molecule, bis(chlorato-O-)carbonyl, (O2ClO)2C=O.

Coordination of 1-methyl-1,3-dihydro-2H-benzimidazole-2-selone to zinc and cadmium: Monotonic and non-monotonic bond length variations for [H(sebenzimMe)]2MCl2 complexes (M = Zn, Cd, Hg)

The reactions of 1-methyl-1,3-dihydro-2H-benzimidazole-2-selone, H(sebenzimMe), towards the zinc and cadmium halides, MX2 (M = Zn, Cd; X = Cl, Br, I), afford the adducts, [H(sebenzimMe)]2MX2, which have been structurally characterized by X-ray diffraction. The halide ligands of each of these complexes participate in hydrogen bonding interactions with the imidazole N–H moieties, although the nature of the interactions depends on the halide. Specifically, the chloride and bromide derivatives, [H(sebenzimMe)]2ZnX2 and [H(sebenzimMe)]2CdX2 (X = Cl, Br), exhibit two intramolecular N–H⋯X interactions, whereas the iodide derivatives, [H(sebenzimMe)]2ZnI2 and [H(sebenzimMe)]2CdI2, exhibit only one intramolecular N–H⋯I interaction. Comparison of the M–Se and M–Cl bond lengths of the chloride series, [H(sebenzimMe)]2MCl2 (M = Zn, Cd, Hg), indicates that while the average M–Cl bond lengths progressively increase as the metal becomes heavier, the variation in M–Se bond length exhibits a non-monotonic trend, with the Cd–Se bond being the longest. These different trends provide an interesting subtlety concerned with use of covalent radii in predicting bond length differences. In addition to tetrahedral [H(sebenzimMe)]2CdCl2, [H(sebenzimMe)]3CdCl2·[H(sebenzimMe)]4CdCl2, which features both five-coordinate and six-coordinate coordinate centers, has also been structurally characterized. Finally, the reaction between CdI2 and H(sebenzimMe) at elevated temperatures affords the 1-methylbenzimidazole complex, [H(sebenzimMe)][H(benzimMe)]CdI2, a transformation that is associated with cleavage of the C–Se bond.

BrCl+ elimination from Coulomb explosion of 1,2-bromochloroethane induced by intense femtosecond laser fields.

By using a dc-slice imaging technique, photodissociation of 1,2-C2H4BrCl was investigated at 800 nm looking for heteronuclear unimolecular ion elimination of BrCl+ in an 80 fs laser field. The occurrence of fragment ion BrCl+ in the mass spectrum verified the existence of a unimolecular decomposition channel of BrCl+ in this experiment. The relative quantum yield of the BrCl+ channel was measured to be 0.8%. By processing and analyzing the velocity and angular distributions obtained from the corresponding sliced images of BrCl+ and its partner ion C2H4+, we concluded that BrCl+ came from Coulomb explosion of the 1,2-bromochloroethane dication 1,2-C2H4BrCl2+. With the aid of quantum chemical calculations at the M06-2X/def2-TZVP level, the potential energy surface for BrCl+ detachment from 1,2-C2H4BrCl2+ has been examined in detail. According to the ab initio calculations, two transition state structures tended to correlate with the reactant 1,2-C2H4BrCl2+ and the products BrCl+ + C2H4+. In this entire dissociation process, the C–Br and C–Cl bond lengths were observed to elongate asymmetrically, that is, the C–Br chemical bond broke firstly, and subsequently a new Br–Cl chemical bond started to emerge while the C–Cl bond continued to exist for a while. Hence, an asynchronous concerted elimination mechanism was favored for BrCl+ detachment.

Spectrum and dissociation properties of fluoro trichloro methane molecule in radiational field

The ozone layer in the stratosphere of the earth’s atmosphere, which can be destroyed by CFC-11 molecule, plays a crucial role in human survival because it can absorb most of the harmful radiation from the sun and effectively protect the earth’s biology. Therefore, it is of evident significance to investigate the properties of CFC-11 molecule. By Motivated by this and the adoption of B3LYP complex function at a level of 6-311++g(3df, 3pd) basis set, we carry out a series of theoretical studies of the Freon material CFC-11 (CFCl3) molecules, including the studies of the equilibrium structure, electric dipole moment, total energy, the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) level, energy gap, infrared and Raman spectrum, C—F dissociation characteristics of CFC-11 molecule, and the effect of the applied electric field on CFC-11 molecule as well. The results show that the maximum error between the theoretical calculation value and the experimental value is less than 2% for an optimized ground state structure; the C—F bond length and C—Cl bond length extend with the increase of electric field intensity, but the degree of change of C—F bond length is much stronger than that of C—Cl; the HOMO energy level and total energy go up and then come down as the external field rises, while the LUMO energy level goes up as the field increases. The energy gap &lt;i&gt;E&lt;/i&gt;&lt;sub&gt;g&lt;/sub&gt; first increases and then decreases with the variation of &lt;i&gt;E&lt;/i&gt;&lt;sub&gt;H&lt;/sub&gt; and &lt;i&gt;E&lt;/i&gt;&lt;sub&gt;L&lt;/sub&gt;. The dipole moment without electric field is a minimum value, and the external electric field leads the molecular polarity to increase and the molecular activity to strengthen. The electric field influences the absorption intensity of infrared and Raman spectrum. The infrared and Raman spectrum move toward the long wave under the action of positive electric field, while they move toward the short wave under the action of negative electric field. The red- or blue-shift of infrared and Raman spectrum occur with the change of electric field. The electric field can be adopted as an auxiliary means to separate the overlapping or quasi-overlapping spectral lines. The potential well depth decreases with the increase of the reverse electric field until it vanishes, which causes the bound state ability of C—F bond of CFC-11 molecule to gradually degrade. This paper is expected to provide a feasible and effective tunable means for the final dissociation and degradation of CFC-11 molecules.

Trans-Bis(2,2′-bipyridine-4,4′-dicarboxylic acid-κ2 N,N′)dichloridoruthenium(III) perchlorate

In the crystal structure of the ruthenium(III) complex, trans-[RuIII(dcbpy)2Cl2]ClO4 (dcbpy = 2,2′-bipyridine-4,4′-dicarboxylic acid, C12H8N2O4), the RuIII atom lies on an inversion centre, showing a small distortion in its octahedral environment. The Ru—Cl bond lengths are shorter than those present in the analogous trans-ruthenium(II) compound containing the bipyridine ligand. The C—O distances in the two symmetry-independent carboxylic acid moieties of the ligand are similar in one group, but different in the other. This is probably due to the different intermolecular interactions they experience with neighbouring cationic complexes. The hydrogen-bonding interactions in which they are involved form a three-dimensional structure, similar to those found in coordination polymers.

A Five-Membered PdSbn Coordination Series

Five complexes of the general formula PdCl2(SbMe2Cl)n (n = 1–5) have been synthesized by combining [PdCl2(MeCN)2] and SbMe2Cl in different molar ratios in toluene. Their solid-state structures have been determined by X-ray crystallography. The complexes display considerable structural diversity: [Pd4Cl8(SbMe2Cl)4] (1, n = 1) is a chloride-bridged tetramer; [Pd2Cl4(SbMe2Cl)4] (2, n = 2) is a dimer; [PdCl(SbMe2Cl)2(SbMe2Cl2)] (3, n = 3) is a supramolecular polymer; [Pd2(SbMe2Cl)8]Cl4 (4, n = 4) is a loosely associated dimer, and [Pd(SbMe2Cl)5]Cl2 (5, n = 5) is a monomer with square-pyramidal PdSb5 coordination geometry. Each structure contains secondary interactions between coordinated Sb centers and chloride ligands or anions, resulting in five-coordinate Sb in all cases with a range of Sb···Cl bond lengths. The electronic structures of these complexes have been investigated using DFT methods including NBO and Pipek–Mezey localized orbital methods in order to interrogate both the Sb–Pd and secondary Sb···C...