Recoil excitation of vibrational structure in the carbon 1s photoelectron spectrum of CF4

The carbon 1s photoelectron spectrum of CF4 measured at photon energies from 330 to 1500 eV shows significant contributions from nonsymmetric vibrational modes. These increase linearly as the photon energy increases. The excitation of these modes, which is not predicted in the usual Franck-Condon point of view, arises from the recoil momentum imparted to the carbon atom in the ionization process. A theory is presented for quantitative prediction of the recoil effect; the predictions of this theory are in agreement to the measurements. The experiments also yield the vibrational frequencies of the symmetric and asymmetric stretching modes in core-ionized CF4, the change in CF bond length upon ionization, -0.61 pm, and the Lorentzian linewidth of the carbon 1s hole, 67 meV.     

Density functional and spin-orbit ab initio study of CF3Br: molecular properties and electronic curve crossing

Quantum chemical calculations of CF(3)Br and the CF(3) radical are performed using density functional theory (DFT) and time-dependent DFT (TDDFT). Molecular structures, vibrational frequencies, dipole moment, bond dissociation energy, and vertical excitation energies of CF(3)Br are calculated and compared with available experimental results. The performance of six hybrid and five hybrid meta functionals in DFT and TDDFT calculations are evaluated. The ωB97X, B3PW91, and M05-2X functionals give very good results for molecular structures, vibrational frequencies, and vertical excitation energies, respectively. The ωB97X functional calculates well the dipole moment of CF(3)Br. B3LYP, one of the most widely used functionals, does not perform well for calculations of the C-Br bond length, bond dissociation energy, and vertical excitation energies. Potential energy curves of the low-lying excited states of CF(3)Br are obtained using the multiconfigurational spin-orbit ab initio method. The crossing point between 2A(1) and 3E states is located near the C-Br bond length of 2.45 ?. Comparison with CH(3)Br shows that fluorination does not alter the location of the crossing point. The relation between the calculated potential energy curves and recent experimental result is briefly discussed.     

The complex spectrum of a "simple" free radical: the Ã-X̃ band system of the jet-cooled boron difluoride free radical

The near-ultraviolet band system of the jet-cooled boron difluoride free radical has been studied by a combination of laser-induced fluorescence and single vibronic level wavelength resolved emission spectroscopies. The radical was produced in a supersonic discharge jet using a precursor mixture of 1%-3% of BF(3) or (10)BF(3) in high pressure argon. A large number of bands were found in the 340-286 nm region and assigned as transitions from the X?(2)A(1) ground state to the lower Renner-Teller component of the A?(2)Π excited state, based on our previous ab initio potential energy surface predictions, matching the emission spectra Franck-Condon profiles of (11)BF(2) and (10)BF(2), and comparison of observed and calculated boron isotope effects. Several bands have been rotationally analyzed providing ground state structural parameters of r(0)(') (BF) = 1.3102(9) ? and θ(0)(') (FBF) = 119.7(6)°. The ground state totally symmetric vibrational energy levels of both boron isotopologues have also been measured and assigned up to energies of more than 8000 cm(-1). Although BF(2) might be considered to be a "simple" free radical, understanding the details of its electronic spectrum remains a major challenge for both theory and experiment.     

Tris(trifluoromethyl)borane carbonyl, (CF3)3BCO-synthesis,physical, chemical and spectroscopic properties,gas phase,and solid state structure

Tris(trifluoromethyl)borane carbonyl, (CF(3))(3)BCO, is obtained in high yield by the solvolysis of K[B(CF(3))(4)] in concentrated sulfuric acid. The in situ hydrolysis of a single bonded CF(3) group is found to be a simple, unprecedented route to a new borane carbonyl. The related, thermally unstable borane carbonyl, (C(6)F(5))(3)BCO, is synthesized for comparison purposes by the isolation of (C(6)F(5))(3)B in a matrix of solid CO at 16 K and subsequent evaporation of excess CO at 40 K. The colorless liquid and vapor of (CF(3))(3)BCO decomposes slowly at room temperature. In the gas phase t(1/2) is found to be 45 min. In the presence of a large excess of (13)CO, the carbonyl substituent at boron undergoes exchange, which follows a first-order rate law. Its temperature dependence yields an activation energy (E(A)) of 112 kJ mol(-)(1). Low-pressure flash thermolysis of (CF(3))(3)BCO with subsequent isolation of the products in low-temperature matrixes, indicates a lower thermal stability of the (CF(3))(3)B fragment, than is found for (CF(3))(3)BCO. Toward nucleophiles (CF(3))(3)BCO reacts in two different ways: Depending on the nucleophilicity of the reagent and the stability of the adducts formed, nucleophilic substitution of CO or nucleophilic addition to the C atom of the carbonyl group are observed. A number of examples for both reaction types are presented in an overview. The molecular structure of (CF(3))(3)BCO in the gas phase is obtained by a combined microwave-electron diffraction analysis and in the solid state by single-crystal X-ray diffraction. The molecule possesses C(3) symmetry, since the three CF(3) groups are rotated off the two possible positions required for C(3)(v)() symmetry. All bond parameters, determined in the gas phase or in the solid state, are within their standard deviations in fair agreement, except for internuclear distances most noticeably the B-CO bond lengths, which is 1.69(2) A in the solid state and 1.617(12) A in the gas phase. A corresponding shift of nu(CO) from 2267 cm(-)(1) in the solid state to 2251 cm(-)(1) in the gas phase is noted in the vibrational spectra. The structural and vibrational study is supported by DFT calculations, which provide, in addition to the equilibrium structure, confirmation of experimental vibrational wavenumbers, IR-band intensities, atomic charge distribution, the dipole moment, the B-CO bond energy, and energies for the elimination of CF(2) from (CF(3))(x)()BF(3)(-)(x)(), x = 1-3. In the vibrational analysis 21 of the expected 26 fundamentals are observed experimentally. The (11)B-, (13)C-, and (19)F-NMR data, as well as the structural parameters of (CF(3))(3)BCO, are compared with those of related compounds.     

Trifluoropropynylxenon(II) tetrafluoroborate [CF3C[triple bond]CXe] [BF4]--isolation of an alkynylxenon(II) compound for the first time

The salt [CF3C[triple bond]CXe] [BF4] was prepared as neat compound by the reaction of the hitherto unknown alkynyldifluoroborane CF3C[triple bond]CBF2 with XeF2 in 1,1,1,3,3-pentafluoropropane (PFP) at -45 degrees C in 59% yield. [CF3C[triple bond]CXe] [BF4] was unambiguously characterised by multinuclear NMR spectroscopy in anhydrous HF (aHF) solution.     

Microwave spectrum, conformation and intramolecular hydrogen bonding of 2,2,2-trifluoroethanethiol (CF3CH2SH)

The microwave spectrum of 2,2,2-trifluoroethanethiol, CF3CH2SH, and of one deuterated species, CF3CH2SD, has been investigated in the 7-80 GHz spectral interval. The microwave spectra of the ground and three vibrationally excited states belonging to three different normal modes of one conformer were assigned for the parent species, and the vibrational frequencies of these fundamentals were determined by relative intensity measurements. Only the ground vibrational state was assigned for the deuterated species. The identified form has a synclinal arrangement for the H-S-C-C chain of atoms and the corresponding dihedral angle is 68(5) degrees from synperiplanar (0 degrees). A weak intramolecular hydrogen bond formed between the thiol (SH) group and one of the fluorine atoms is stabilizing this conformer. There is no evidence in the microwave spectrum for the H-S-C-C antiperiplanar form. The hydrogen atom of the thiol group should have the ability to tunnel between two equivalent synclinal potential wells, but no splittings of spectral lines due to tunneling were observed. The microwave work was augmented by quantum chemical calculations at the B3LYP/aug-cc-pVTZ and MP2/aug-cc-pVTZ levels of theory.     

The singlet-triplet separation in CF2: state-of-the-art ab initio calculations and Franck-Condon simulations including anharmonicity.

Geometrical parameters, vibrational frequencies and relative electronic energies of the X2B1 state of CF2- and the X1A1 and ?3B1 states of CF2 have been calculated. Core-electron effects on the computed minimum-energy geometries and relative electronic energies have been investigated, and relativistic contributions to the computed relative electronic energies calculated. Potential energy functions of the X2B1 state of CF2- and the X1A1 and ?3B1 states of CF2 have been determined, and anharmonic vibrational wavefunctions of these states calculated variationally. Franck-Condon factors including anharmonicity and Duschinsky rotation have been computed and used to simulate the ?-X emission spectrum of CF2 determined by S. Koda [Chem. Phys. Lett. 1978, 55, 353] and the 364 nm laser photodetachment spectrum of CF2- obtained by R. L. Schwartz et al. [J. Phys. Chem. A 1999, 103, 8213]. Comparison between theory and experiment shows that the theoretical approach benchmarked in the present study is able to give highly reliable positions for the CF2(X1A1) + e <-- CF2-(X2B1) and CF2(?3B1) + e <-- CF2-(X2B1) bands in the photoelectron spectrum of CF2- and a reliable singlet-triplet gap for CF2. It is therefore concluded that the same theoretical approach should give reliable simulated CCl2(X1A1) + e <-- CCl2-(X2B1) and CCl2(?3B1) + e <-- CCl2-(X2B1) bands in the photodetachment spectrum of CCl2- and a reliable singlet-triplet gap for CCl2.     

Reversible skeletal transmetalations of inorganic rings: isolation of aluminatophosphazenes, a zwitterionic phosphazene, and a donor-stabilized alumazine-phosphazene hybrid cation

Synthesis of the cyclic aluminatophosphazene ring N(PCl2NMe)2AlMeCl (5) has been achieved via a skeletal transmetalation reaction between AlMe3 and the boratophosphazene N(PCl2NMe)2BCl2 (1). Reaction of 5 with various halogenated Lewis acids such as GaCl3 yielded the fully chlorinated aluminum heterocycle N(PCl2NMe)2AlCl2 (8) through a methyl-halogen exchange process. In contrast, treatment of 5 with excess AlMe3 resulted in complete methylation at aluminum to give N(PCl2NMe)2AlMe2 (6). Compound 5 was reacted with various Ag+ salts with weakly coordinating anions, including Ag[OSO2CF3], which afforded the triflate-substituted heterocycle N(PCl2NMe)2AlMe(OSO2CF3) (9). The reaction of 5 with Ag[BF4] surprisingly produced the previously known fluorinated boratophosphazene N(PCl2NMe)2BF2 (10). The transformation of 1 to 5 and then to 10 represents a rare, formally reversible, skeletal transmetalation process involving boron and aluminum. Treatment of 5 with Ag[PF6] led to the insertion of phosphorus in place of aluminum to form the novel zwitterionic fluorinated phosphorus(V) heterocycle N(PCl2NMe)2PF4 (11). The ethyl-substituted aluminatophosphazene N(PCl2NMe)2AlMeEt (14) reacted cleanly with a 1:1 mixture of [Ph3C][B(C6F5)4] and THF to give the novel donor-stabilized alumazine-phosphazene hybrid cation, [7.THF]+, as the [B(C6F5)4]- salt [N(PCl2NMe)2AlMe.THF][B(C6F5)4] (15).     

Rearrangement reactions of the transient lewis acids (CF(3))(3)B and (CF(3))(3)BCF(2): an experimental and theoretical study

Short-lived (CF(3))(3)B and (CF(3))(3)BCF(2) are generated as intermediates by thermal dissociation of (CF(3))(3)BCO and F(-) abstraction from the weak coordinating anion [B(CF(3))(4)](-), respectively. Both Lewis acids cannot be detected because of their instability with respect to rearrangement reactions at the B-C-F moiety. A cascade of 1,2-fluorine shifts to boron followed by perfluoroalkyl group migrations and also difluorocarbene transfer reactions occur. In the gas phase, (CF(3))(3)B rearranges to a mixture of linear perfluoroalkyldifluoroboranes C(n)()F(2)(n)()(+1)BF(2) (n = 2-7), while the respective reactions of (CF(3))(3)BCF(2) result in a mixture of linear (n = 2-4) and branched monoperfluoroalkyldifluoroboranes, e.g., (C(2)F(5))(CF(3))FCBF(2). For comparison, the reactions of [CF(3)BF(3)](-) and [C(2)F(5)BF(3)](-) with AsF(5) are studied, and the products in the case of [CF(3)BF(3)](-) are BF(3) and C(2)F(5)BF(2) whereas in the case of [C(2)F(5)BF(3)](-), C(2)F(5)BF(2) is the sole product. In contrast to reports in the literature, it is found that CF(3)BF(2) is too unstable at room temperature to be detected. The decomposition of (CF(3))(3)BCO in anhydrous HF leads to a mixture of the new conjugate Br?nsted-Lewis acids [H(2)F][(CF(3))(3)BF] and [H(2)F][C(2)F(5)BF(3)]. All reactions are modeled by density functional calculations. The energy barriers of the transition states are low in agreement with the experimental results that (CF(3))(3)B and (CF(3))(3)BCF(2) are short-lived intermediates. Since CF(2) complexes are key intermediates in the rearrangement reactions of (CF(3))(3)B and (CF(3))(3)BCF(2), CF(2) affinities of some perfluoroalkylfluoroboranes are presented. CF(2) affinities are compared to CO and F(-) affinities of selected boranes showing a trend in Lewis acidity, and its influence on the stability of the complexes is discussed. Fluoride ion affinities are calculated for a variety of different fluoroboranes, including perfluorocarboranes, and compared to those of the title compounds.     

On the correlation between bond-length change and vibrational frequency shift in hydrogen-bonded complexes: a computational study of Y...HCl dimers (Y = N2, CO, BF)

The H-Cl bond-length change and the harmonic vibrational frequency shift of the H-Cl stretch on formation of the linear isoelectronic Y...H-Cl complexes (Y = N(2), CO, BF) have been determined by ab initio computations at different levels of theory. These shifts are in agreement with predictions from a model based on perturbation theory and involving the first and second derivatives of the interaction energy with respect to displacement of the H-Cl bond length from its equilibrium value in the isolated monomer. At the highest level of theory, blue shifts were obtained for BF...HCl and CO...HCl, while red shifts were obtained for FB...HCl, OC...HCl, and N(2)...HCl. These vibrational characteristics are rationalized by considering the balance between the interaction energy derivatives obtained from the perturbative model. The widely believed correlation between the bond-length change and the sign of the frequency shift obtained on complexation is discussed and found to be unreliable.     

The photodissociation reaction dynamics of CF(3)I at 304 nm ((3)Q(0+), (1)Q(1)<--(3)Q(0+), and (3)Q(1))

The photodissociation of CF(3)I at 304 nm has been studied using long time-delayed core-sampling photofragment translational spectroscopy. Due to its capability of detecting the kinetic energy distribution of iodine fragments with high resolution, it is able to directly assign the vibrational state distribution of CF(3) fragments. The vibrational state distributions of CF(3) fragments in the I(*)((2)P(12)) channel, i.e., (3)Q(0+) state, have a propensity of the nu(2) (') umbrella mode with a maximum distribution at the vibrational ground state. For the I((2)P(32)) channel, i.e., (1)Q(1)<--(3)Q(0+), the excitation of the nu(2) (') umbrella mode accounts for the majority of the vibrational excitation of the CF(3) fragments. The 1 nu(1) (') (symmetric CF stretch) +nnu(2) (') combination modes, which are associated with the major progression of the nu(2) (') umbrella mode, are observed for the photodissociation of CF(3)I at the I channel, i.e., (3)Q(1) state. The bond dissociation energy of the CI bond of CF(3)I is determined to be D(0)(CF(3)-I)相似文献   

Theoretical study of the [2+3] cycloaddition of nitrones to nitriles-influence of nitrile substituent,solvent and Lewis acid coordination

The [2+3] cycloaddition of nitrone PhCHdoublebondN(Me)O to nitriles RCtriplebondN (R=Me, Ph, CF(3)) was studied using quantum chemical calculations at the HF/6-31G* and B3LYP/6-31G* level of theory. With MeCN and PhCN, the reaction occurs through a concerted mechanism and leads selectively to Delta(4)-1,2,4-oxadiazolines rather than Delta(2)-1,2,5-oxadiazolines. Electron withdrawing substituents such as CF(3) at the nitrile provoke a non-synchronous bond formation, with the C-O bond being established on an earlier stage than the C-N bond. Additionally, the reaction becomes thermodynamically and kinetically more favourable. In the reaction of adducts of MeCN with BH(3) or BF(3) as model Lewis acids, the mechanism was found to change from fully concerted in the case of free MeCN towards a two-step reaction in the presence of BF(3), in which C-O bond formation occurs first. The BH(3)-mediated reaction occupies an intermediate stage where ring formation occurs in one-step but non-simultaneously, similar to the reaction of CF(3)CN. Interaction of the Lewis acid with the nitrile in the course of the reaction facilitates the cycloaddition by stabilizing transition states, intermediate and product rather than by activating the nitrile. The solvent influences the organic reaction mainly by lowering the energy of the reagents, thus leading to a higher activation barrier in a more polar solvent. In the Lewis acid mediated reaction, in contrast, the intermediate is strongly stabilised by a polar solvent and with that the synchronicity of the reaction changes in favour of a two-step mechanism.     

Chemical insights from high-resolution X-ray photoelectron spectroscopy and ab initio theory: propyne, trifluoropropyne, and ethynylsulfur pentafluoride.

High-resolution carbon 1s photoelectron spectroscopy of propyne (HC triple bond CCH3) shows a spectrum in which the contributions from the three chemically inequivalent carbons are clearly resolved and marked by distinct vibrational structure. This structure is well accounted for by ab initio theory. For 3,3,3-trifluoropropyne (HC triple bond CCF3) and ethynylsulfur pentafluoride (HC triple bond CSF5), the ethynyl carbons show only a broad structure and have energies that differ only slightly from one another. The core-ionization energies can be qualitatively understood in terms of conventional resonance structures; the vibrational broadening for the fluorinated compounds can be understood in terms of the effects of the electronegative fluorines on the charge distribution. Combining the experimental results with gas-phase acidities and with ab initio calculations provides insights into the effects of initial-state charge distribution and final-state charge redistribution on ionization energies and acidities. In particular, these considerations make it possible to understand the apparent paradox that SF5 and CF3 have much larger electronegativity effects on acidity than they have on carbon 1s ionization energies.     

Thermally stable perfluoroalkylfullerenes with the skew-pentagonal-pyramid pattern: C60(C2F5)4O, C60(CF3)4O, and C60(CF3)6

Reaction of C(60) with CF(3)I at 550 degrees C, which is known to produce a single isomer of C(60)(CF(3))(2,4,6) and multiple isomers of C(60)(CF(3))(8,10), has now been found to produce an isomer of C(60)(CF(3))(6) with the C(s)-C(60)X(6) skew-pentagonal-pyramid (SPP) addition pattern and an epoxide with the C(s)-C(60)X(4)O variation of the SPP addition pattern, C(s)-C(60)(CF(3))(4)O. The structurally similar epoxide C(s)-C(60)(C(2)F(5))(4)O is one of the products of the reaction of C(60) with C(2)F(5)I at 430 degrees C. The three compounds have been characterized by mass spectrometry, DFT quantum chemical calculations, Raman, visible, and (19)F NMR spectroscopy, and, in the case of the two epoxides, single-crystal X-ray diffraction. The compound C(s)-C(60)(CF(3))(6) is the first [60]fullerene derivative with adjacent R(f) groups that are sufficiently sterically hindered to cause the (DFT-predicted) lengthening of the cage (CF(3))C-C(CF(3)) bond to 1.60 A as well as to give rise to a rare, non-fast-exchange-limit (19)F NMR spectrum at 20 degrees C. The compounds C(s)-C(60)(CF(3))(4)O and C(s)-C(60)(C(2)F(5))(4)O are the first poly(perfluoroalkyl)fullerene derivatives with a non-fluorine-containing exohedral substituent and the first fullerene epoxides known to be stable at elevated temperatures. All three compounds demonstrate that the SPP addition pattern is at least kinetically stable, if not thermodynamically stable, at temperatures exceeding 400 degrees C. The high-temperature synthesis of the two epoxides also indicates that perfluoroalkyl substituents can enhance the thermal stability of fullerene derivatives with other substituents.     

A new route to coordination complexes of nitroxyl (HN=O) via insertion reactions of nitrosonium triflate with transition-metal hydrides

Nitrosonium triflate reacts with cold methylene chloride solutions of mer,trans-ReH(CO)3(PPh3)2 (1) with 1,1-insertion of NO+ into the Re-H bond to give the orange nitroxyl complex [mer,trans-Re(NH=O)(CO)3(PPh3)2][SO3CF3] (3) in 86% isolated yield. Use of [NO][PF6] or [NO][BF4] gives analogous insertion products at low temperature, which decompose on warning to ambient temperature to the fluoride complex mer,trans-ReF(CO)3(PPh3)2 (4). A related 1,1-insertion is observed in the reaction of 1 with [PhN2][PF6] in acetone that affords the yellow-orange phenyldiazene salt [mer,trans-Re(NH=NPh)(CO)3(PPh3)2][PF6] (2), which has been characterized by X-ray crystallographic methods. The methyl derivative mer,trans-Re(CH3)(CO)3(PPh3)2 (5) also undergoes a 1,1-insertion reaction with [NO][SO3CF3] to give the nitrosomethane adduct [mer,trans-Re{N(CH3)=O}(CO)3(PPh3)2][SO3CF3] (6) as red crystals in 75% yield. The nitroxyl complex [cis,trans-OsBr(NH=O)(CO)2(PPh3)2][SO3CF3] (8) can be similarly prepared as orange crystals in 52% yield by reaction of cis,trans-OsHBr(CO)2(PPh3)2 (7) with [NO][SO3CF3] in cold methylene chloride solution.     

Experimental and theoretical studies of the vibrational and electronic spectra of a lanthanide ion at a site of T(h) symmetry: Pr3+ in Cs2NaPr(NO2)6

The Pr(3+) ion in Cs(2)NaPr(NO(2))(6) is situated at a site of T(h) symmetry with 12-coordination to O atoms of bidentate nitrito groups. First-principles calculations of the vibrational modes of the complex were carried out using the density functional theory with the generalized gradient approximation Perdew-Burke-Ernzerhof exchange-correlation functional. The calculations that treated the Pr(3+) 4f electrons as valence electrons showed better agreement with the experimental vibrational assignments compared with those treating the 4f electrons a part of the inner core. The (1)D(2) → (3)H(4) emission spectra of Cs(2)NaPr(NO(2))(6) at 7 K enabled assignments to be made for the crystal-field (CF) levels of the ground-state multiplet. The emission of the dilute system Cs(2)NaY(NO(2))(6):Pr(3+) was dominated by NO(2)(-) triplet emission, which was quenched at elevated temperatures by energy transfer to trace Eu(3+) impurity. From magnetic dipole calculations and the vibronic fingerprint, detailed assignments are given for the complex 10 K electronic absorption spectrum of Cs(2)NaPr(NO(2))(6) between 3940 and 18800 cm(-1), and the derived Pr(3+) 4f(2) energy-level data set has been fitted by calculation. By comparison with Cs(2)NaPrCl(6), the fourth-order CF parameter in Cs(2)NaPr(NO(2))(6) is relatively small so that interaction with a 4fnp configuration is not important. From the NO(2)(-) absorption bands above 20,000 cm(-1), the N-O bond length change upon excitation is small, whereas the angle O-N-O opens by more than 10° in the triplet state. By contrast to the NO(2)(-) internal vibration frequencies, which except for the wagging mode show only minor changes with the environment, the triplet-state energy shows a linear decrease with an increase of the lanthanide (Ln(3+)) ionic radius in Cs(2)NaLn(NO(2))(6). Using the eigenvectors from the energy-level fit, the variation of the inverse magnetic susceptibility with temperature has been calculated between 1 and 100 K and the values are somewhat lower than those from experiment.     

Molecular docking studies,structural and spectroscopic properties of monomeric and dimeric species of benzofuran-carboxylic acids derivatives: DFT calculations and biological activities

Structural optimization, molecular docking analysis, electronic and vibrational properties have been investigated for the 1-benzofuran-2-carboxylic acid (2BF) and 1-benzofuran-3-carboxylic acid (3BF) using DFT/B3LYP/6-311++G(d,p) level of theory. The theoretical parameters have a very good consistency with the experimental ones. The weak intermolecular interactions were analyzed by different tool such as: Hirshfeld surfaces, topological analysis and natural bond orbital studies. The nonlinear optical properties have been investigated. Molecular electrostatic potential and frontier molecular orbitals (FMOs) analysis have been carried out to understand the reactivity of the molecule. In addition, TD-DFT calculation is initiated to simulate the UV–vis absorption spectrum and to determine several important electronic properties like HOMO-LUMO gap energy and electronic transitions. The complete vibrational assignments and the force constants were reported for monomer and dimers of both acids. The biological activities of the tow acids have been studied via molecular docking analysis. The later calculations prove that the studied acids have an inhibitor effect against cancer and microbial diseases.     

Formation of hexacarbonylmanganese(I) salts, [Mn(CO)6]+X-, in anhydrous HF

A convenient one-step synthesis for [Mn(CO)6]+ salts has been developed. The method involves the one-electron oxidation of Mn2(CO)10 by protons in solutions of Lewis acids (BF3, (CF3)3BCO) and anhydrous HF. The molecular structure of [Mn(CO)6][BF4].SO2 was determined by single-crystal X-ray diffraction. Crystal data: orthorhombic, space group Cmc2(1); a = 8.7001(2) A, b = 11.8497(3) A, and c = 11.7437(3) A; Z = 4; R1 = 0.0320 and wR2 = 0.1106. The structural, NMR, and vibrational spectroscopic properties of [Mn(CO)6]+ fit perfectly with those of the isoelectronic species [V(CO)6]-, Cr(CO)6, and [Fe(CO)6]2+.     

Tetrasulfur, S4: rotational spectrum, interchange tunneling, and geometrical structure

The rotational spectrum of S4 has been observed for the first time in an electrical discharge through sulfur vapor. Two techniques have been used: Fourier transform microwave spectroscopy and long-path millimeter-wave absorption spectroscopy. Small, but systematic shifts of the measured transition frequencies of the normal isotopic species indicate that S4 has C2v symmetry but with a low-lying transition state of D2h symmetry, yielding interchange tunneling at 14.1(2) kHz in its ground vibrational state. From the rotational constants of the normal and the single 34S isotopic species, an experimental (r0) structure has been derived: S4 is a singlet planar trapezoid with a terminal bond length of 1.899(7) A, a central bond of 2.173(32) A, and an S-S-S angle of 103.9(8) degrees. Like thiozone (S3), S4 is a candidate for detection in the atmosphere of the Jovian moon Io and in other astronomical sources.     

Fluoroformyl trifluoroacetyl disulfide, FC(O)SSC(O)CF3: synthesis, structure in solid and gaseous states, and conformational properties

Fluoroformyl trifluoroacetyl disulfide, FC(O)SSC(O)CF3, is prepared by quantitative reaction between FC(O)SCl and CF(3)C(O)SH. The conformational properties and geometric structure of the gaseous molecule have been studied by vibrational spectroscopy (IR(gas), Raman(liquid), IR(matrix)), gas electron diffraction (GED), and quantum chemical calculations (B3LYP and MP2 methods). The disulfide bond length derived from the GED analysis amounts 2.023(3) Angstroms, and the dihedral angle around this bond, phi(CS-SC), is 77.7(21) degrees, being the smallest dihedral angle measured for noncyclic disulfides in the gas phase. The compound exhibits a conformational equilibrium at room temperature having the most stable form C(1) symmetry with a synperiplanar (sp-sp) orientation of both carbonyl groups with respect to the disulfide bond. A second form was observed in IR spectra of the Ar matrix isolated compound at cryogenic temperatures, corresponding to a conformer that possess the carbonyl bond of the FC(O) moiety in antiperiplanar position with respect to the S-S single bond (ap-sp). A DeltaH degrees = - = 1.34(11) kcal/mol has been determined by IR(matrix) spectroscopy. The structure of single crystal of FC(O)SSC(O)CF3 was determinate by X-ray diffraction analysis at low temperature using a miniature zone melting procedure. The crystalline solid (monoclinic, P2(1)/n, a = 5.240(4)Angstroms, b = 23.319(17)Angstroms, c = 6.196(4)Angstroms, beta = 113.14(3) degrees) consists exclusively of the (sp-sp) conformation. The geometrical parameters agree with those obtained for the molecule in the gas phase.