Iron-Iridium Mixed-Metal Carbonyl Clusters: A Mössbauer Study of the Structure and of the Adsorption of [Fe2Ir2(CO)12]2− on MgO

¹⁹³Ir and ⁵⁷Fe Mössbauer spectroscopy was used to investigate the structure of the [Fe₂Ir₂(CO)₁₂]^2- cluster compound and the adsorption of this cluster on hydrated MgO. Supported samples were prepared by impregnation of the magnesia with solutions of [Et₄N]₂[Fe₂Ir₂(CO)₁₂] in acetone. The Mössbauer and FT-IR spectra of the MgO-supported cluster confirm that the bimetallic carbonyl is molecularly physisorbed onto MgO without undergoing any transformation or decomposition. The easy solvent extraction of the intact cluster from the oxide surface excludes ion pairing between the cluster anion and the Mg²⁺ surface sites. Mössbauer spectra are in agreement with the refined structure of the molecular cluster and the temperature dependence of the ⁵⁷Fe Mössbauer spectra above 80 K is consistent with the low degree of interaction of the cluster with the support. This technique, therefore, appears to be promising in order to infer structural information when X-ray determination fails.     

Mechanism of formation and decay of the compound nuclei150Gd produced by two entrance channels (16O+134Ba) and (40Ar+110Pd)

Excitation functions have been drawn for evaporation residues issued from¹⁵⁰Gd, a compound nucleus produced either by¹⁶O ions on¹³⁴Ba, or by⁴⁰Ar on¹¹⁰Pd. Absolute cross sections were measured for^145–147Gd,^145–147Eu,^141m Sm,^143m Sm,^140m Pm and^139m Nd. Complete fusion cross sections have been obtained and compared to calculated estimations based, at low energies, on the simple expressionσ _CF=πR _Fuss ² (1?V _Fus/E) whereR _Fus andV _Fus are respectively the distance and the potential for fusion atdV/dr=0. For high energies σ_CF=πR _cr ² (1?V_cr/E) with the model of critical distanceR _cr and critical potentialV _cr. Thresholds energies have been determined with a particular care. The analysis of the shape and the width of excitation functions, particularly for the emission of 4 and 5 neutrons, has been carried out and compared to calculated values. The difference between argon and oxygen induced reactions has been attributed to the difference inl population in the entrance channel.     

Enhancement of combinatorial chemistry by microwave-assisted organic synthesis

It was in the 1980 s that the first papers in which the use of either combinatorial methods or microwave heating in organic chemistry were published. Unlike combinatorial chemistry, which quite readily became an accepted method, particularly in the pharmaceutical industry, it is only now that microwave heating is truly gaining acceptance. Our aim in this review is to attempt to rationalize this slow acceptance and to show the benefits to be gained by employing microwave heating in tandem with combinatorial chemistry. We will also give a number of examples of successful applications.     

(Z)-3-p-tolylsulfinylacrylonitrile as a chiral dienophile: diels-alder reactions with furan and acyclic dienes

The behavior of (Z)-3-p-tolylsulfinylacrylonitrile (1) as a chiral dienophile has been evaluated from its reactions with furan and acyclic dienes. Electrostatic interactions of the cyano group with the sulfinyl one restrict the conformational mobility around the C-S bond, thus controlling the pi-facial selectivity, which is almost complete in all cases, the approach of the diene from the less-hindered face of the dienophile (that bearing the lone electron pair) in the predominant rotamer being the favored one. The regioselectivity is also completely controlled by the cyano group. Additionally, the reactivity of compound 1 as well as its endo-selectivity are both higher than those observed for the corresponding (Z)-3-sulfinylacrylates, thus proving the potential of sulfinylnitriles as chiral dienophiles.     

Enthalpies of solvation for N-alkylamides in water and in carbon tetrachloride at 25°C

Molar enthalpies of solution at infinite dilution have been determined at 25°C for several N-alkyl and N,N-dialkylamides in water and in carbon tetrachloride, using a Calvet-type rotating calorimeter, and solution concentrations below 5×10^–2 molal. Relevant enthalpies of transfer between the two solvents also have been derived. Molar enthalpies of solvation have been obtained by adding enthalpies of vaporization to solution values. Results are compared with those of other laboratories on other substituted amides, and their dependence on the number of carbon atoms in the chain is discussed. A possible computation of solvation enthalpies of functional groups is suggested and results for hydration of peptide or similar groups present in the compounds examined are discussed in terms of current models of their hydration and hydrogen bond formation.Presented at the sixth Italian meeting on Calorimetry and Thermal Analysis (AICAT) held in Naples, December 4–7, 1984.     

Open-shell localized Hartree-Fock method based on the generalized adiabatic connection Kohn-Sham formalism for a self-consistent treatment of excited states

An effective exact-exchange Kohn-Sham approach for the treatment of excited electronic states, the generalized adiabatic connection open-shell localized Hartree-Fock (GAC-OSLHF) method is presented. The GAC-OSLHF method is based on the generalized adiabatic connection Kohn-Sham formalism and therefore capable of treating excited electronic states, which are not the energetically lowest of their symmetry. The method is self-interaction free and allows for a fully self-consistent computation of excited valence as well as Rydberg states. Results for atoms and small- and medium-size molecules are presented and compared to restricted open-shell Hartree-Fock (ROHF) and time-dependent density-functional results as well as to experimental data. While GAC-OSLHF and ROHF results are quite close to each other, the GAC-OSLHF method shows a much better convergence behavior. Moreover, the GAC-OSLHF method as a Kohn-Sham method, in contrast to the ROHF approach, represents a framework which allows also for a treatment of correlation besides an exchange by appropriate functionals. In contrast to the common time-dependent density-functional methods, the GAC-OSLHF approach is capable of treating doubly or multiply excited states and can be easily applied to molecules with an open-shell ground state. On the nodal planes of the energetically highest occupied orbital, the local multiplicative GAC-OSLHF exchange potential asymptotically approaches a different, i.e., nonzero, value than in other regions, an asymptotic behavior which is known from exact Kohn-Sham exchange potentials of ground states of molecules.     

Structure and conformations of N-(fluoroformyl)imidosulfurous dichloride,FC(O)N=SCl2

The IR (gas) and Raman (liquid) spectra of FC(O)NSCl(2) demonstrate the presence of a conformational mixture in both phases. According to a gas electron diffraction study, the main conformer (94(8)%) possesses a syn-syn structure (C(O)F group synperiplanar with respect to the SCl(2) bisector and the C=O bond synperiplanar to the N=S bond). Quantum chemical calculations (HF, B3LYP and MP2 with 6-31G basis set, and MP2/6-311(2df)) predict a syn-anti structure for the second conformer. Analysis of the IR (gas) spectrum results in a contribution of 5(1)% of the minor form, corresponding to a Gibbs free energy difference DeltaG degrees = G degrees (syn-anti) - G degrees (syn-syn) = 1.75(15) kcal/mol. This value is reproduced very well by quantum chemical calculations, which include electron correlation effects (DeltaG degrees = 1.28-1.56 kcal/mol). The HF approximation overestimates this energy difference (DeltaG degrees = 3.24 kcal/mol).     

Trifluoroacetylsulfenyl trifluoroacetate,CF(3)C(O)-S-O-C(O)CF(3), a novel compound with a symmetrically substituted S-O bond: synthesis,spectroscopic characterization,and quantum chemical calculations

The new compound trifluoroacetylsulfenyl trifluoroacetate, CF(3)C(O)SOC(O)CF(3), which possesses two identical carbonyl substituents attached to the S-O bond, has been synthesized. The IR and UV spectra of the gas phase as well as the (13)C NMR spectrum of the solution in CDCl(3) were recorded and assigned. Quantum chemical calculations were performed with the ab initio methods HF and MP2 and the density functional approach B3LYP. The 6-31G basis set was chosen in all calculations. The molecule possesses a skew structure, and according to all computational methods, the syn-syn structure (C=O bonds of both C(O)CF(3) groups synperiplanar to S-O bond) represents the most stable conformer. In agreement with the quantum chemical calculations, the presence of small amounts (< or =5%) of a second conformer (anti-syn) cannot be excluded on the basis of the IR spectrum. The calculated values for the torsional angle around the S-O bond (delta(C-S-O-C)) of the syn-syn form are smaller than 80 degrees (72-78 degrees). Comparison with theoretical results for the corresponding disulfide CF(3)C(O)SSC(O)CF(3) and peroxide CF(3)C(O)OOC(O)CF(3) indicates that the structural properties of sulfenyl compounds are more similar to those of disulfides than to those of peroxides.     

Novel selenium-containing non-natural diamino acids

The general synthesis of a new class of non-natural diamino acids, 2-amino-3-[(2′-aminoalkyl)seleno]propanoic acids, or Se-(aminoalkyl)selenocysteines, is reported. Under the conditions devised, enantiopure N-Boc-protected β-l-iodoamines, which are readily generated from proteinogenic α-amino acids, were treated with the selenolate anion obtained from NaBH₄ splitting of the Se-Se bond in commercial l-selenocystine. The Se-alkylation products were enantiomerically pure and the reaction is high yielding (92-98%), without any detectable traces of accompanying by-products.