Secondary bonding in para-substituted diphenyltellurium dichlorides (p-XC6H4)2TeCl2 (X = H, Me, MeO) probed by 125Te MAS NMR spectroscopy. Crystal and molecular structure of (p-MeC6H4)2TeCl2

The solid-state structures of the previously known para-substituted diphenyltellurium dichlorides, (p-XC₆H₄)₂TeCl₂ (X=H (1), Me (2), MeO (3)) were investigated by ¹²⁵Te MAS NMR spectroscopy and in case of 2 by single crystal X-ray diffraction. The ¹²⁵Te-NMR shielding anisotropy (SA) was studied by tensor analyses based on relative intensities of the observed spinning sidebands. Solid-state NMR parameters, namely the isotropic chemical shift (δ_iso), anisotropy (ζ) and asymmetry (η), were discussed in relation to the molecular structures established by X-ray crystallography. The asymmetry (η) was found to be particularly sensitive to structural differences stemming mostly from the diverse secondary Te...Cl interactions, but no correlation with geometric parameters could be established.

Synthesis and molecular structure of [n-Bu2(F)SnOSn(F)t-Bu2]2 - an unsymmetrically substituted tetraorganodistannoxane

The dimeric tetraorganodistannoxane [n-Bu₂(F)SnOSn(F)t-Bu₂]₂ (1) was prepared by the reaction of (t-Bu₂SnO)₃ with n-Bu₂SnF₂ and characterized in solution by multinuclear NMR spectroscopy and ESI MS spectrometry and in the solid state by ¹¹⁹Sn MAS NMR spectroscopy and single crystal X-ray diffraction.

Steric control over molecular structure and supramolecular association exerted by tin- and ligand-bound groups in diorganotin carboxylates

Structural data (X-ray and solution and solid-state ^₁₁₉Sn NMR) show that skew-trapezoidal-bipyramidal diorganotin compounds of 2-quinaldate are invariably monomeric, owing to the steric bulk of the carboxylate ligand. In contrast, most of the analogous compounds of 2-picolinate (2-pic) can increase their coordination number by polymerization or the incorporation of solvent in their coordination sphere in the solid state. The exceptional compound is tBu₂Sn(2-pic)₂ (3), for which no increase in coordination number is apparent, a result that is correlated with the bulky tert-butyl groups. Thus, judicious choice of tin or ligand substituents can be exploited to dictate coordination number and/or the degree of supramolecular aggregation in the investigated systems.

Synthesis, molecular structure, and isomerisation in solution of (Me3SbS)2Me2SnCl2. Concomitant hypercoordination of tin and antimony

The reaction of Me₃SbCl₂ and (Me₂SnS)₃ afforded the complex (Me₃SbS)₂Me₂SnCl₂ in high yields, whose molecular structure features both hypercoordinated tin and antimony atoms. In solution, (Me₃SbS)₂Me₂SnCl₂ undergoes a reversible dissociation and ligand interchange reaction to give Me₃SbS, Me₃SbCl₂ and (Me₂SnS)₃.

A new method for locating the global optimum : application of the cutting angle method to molecular structure prediction

Many problems in chemistry depend on the ability to identify the global minimum or maximum of a function. Examples include applications in chemometrics, optimization of reaction or operating conditions, and non-linear least-squares analysis. This paper presents the results of the application of a new method of deterministic global optimization, called the cutting angle method (CAM), as applied to the prediction of molecular geometries. CAM is shown to be competitive with other global optimization techniques for several benchmark molecular conformation problem. CAM is a general method that can also be applied to other computational problems involving global minima, global maxima or finding the roots of nonlinear equations.

Challenges of continuous global optimization in molecular structure prediction

The molecular geometry, the three dimensional arrangement of atoms in space, is a major factor determining the properties and reactivity of molecules, biomolecules and macromolecules. Computation of stable molecular conformations can be done by locating minima on the potential energy surface (PES). This is a very challenging global optimization problem because of extremely large numbers of shallow local minima and complicated landscape of PES. This paper illustrates the mathematical and computational challenges on one important instance of the problem, computation of molecular geometry of oligopeptides, and proposes the use of the Extended Cutting Angle Method (ECAM) to solve this problem.

ECAM is a deterministic global optimization technique, which computes tight lower bounds on the values of the objective function and fathoms those part of the domain where the global minimum cannot reside. As with any domain partitioning scheme, its challenge is an extremely large partition of the domain required for accurate lower bounds. We address this challenge by providing an efficient combinatorial algorithm for calculating the lower bounds, and by combining ECAM with a local optimization method, while preserving the deterministic character of ECAM.

Ionic liquid mixtures—variations in physical properties and their origins in molecular structure

In order to explore the various possible property trends in ionic liquid mixtures, five different ionic liquids were mixed with N-methyl-N-propylpyrrolidinium bis(trifluoromethylsulfonyl)amide ([C₃mpyr][NTf₂]), and the viscosities, excess molar volumes, ionic conductivities, and phase diagrams of the mixtures were determined over a range of temperatures. In a number of the mixtures the crystallization of both components was completely suppressed and no melting point was observable. Such mixtures of similar ionic liquids thus have potential for use in low-temperature applications by extending the liquid range to T_g. The molar conductivities and viscosities are described as approximating predictable or “simple” mixing behaviors, while excess molar volumes were found to show a variety of mixing and nonideal mixing effects. Mixture equations for viscosity and conductivity are discussed and analyzed. An immiscibility window was observed in the trihexyl(tetradecyl)phosphonium bis(trifluoromethylsulfonyl)amide ([P_6,6,6,14][NTf₂]) in the [C₃mpyr][NTf₂] system in the [C₃mpyr][NTf₂]-rich region. Unusual physical properties are exhibited by miscible compositions near the demixing line. These compositions are described as [P_6,6,6,14][NTf₂]-like, even up to 0.5 mol fraction of [C₃mpyr][NTf₂].

Crystal structure of (4-bromonaphthalen-2-yl) acetonitrile, C12H8BrN

C_I2H₈BrN, monoclinic, Pl2₁/cl (No. 14), a = 7.555(6) Å, b =7.727(3) Å, c =16.643(2) Å, β =98.95(2)°, V =959.8 ų , Z =4, R_gt(F) =0.033, wRref(F²) =0.097, T =173 K.

Synthesis and structure of tris(triphenyltin)benzene-1,3,5-tricarboxylate and its tri-DMSO adduct

The molecular structure of (Ph₃SnO₂C)₃C₆H₃ reveals distorted tetrahedral C₃O geometries for each tin atom. No intermolecular Sn...O associations occur between the molecules so that the trinuclear molecule may be considered monomeric. An increase in coordination number at tin is indicated by ¹¹⁹Sn NMR measurements conducted in d₆-DMSO solution and this has been confirmed by a structure analysis of (DMSO·Ph₃SnO₂C)₃C₆H₃·2 DMSO. In this structure, the tin atom geometries are distorted trigonal bipyramidal, existing within trans-C₃O₂ donor sets. Thus, while is it possible for the tin atoms to increase their coordination numbers in (Ph₃SnO₂C)₃C₆H₃, molecular aggregation to form polymeric arrays is precluded, most likely due to steric constraints.

A spacer-linked molecular diorganotin oxide

The synthesis and molecular structure are reported of the first example of a diorganotin oxide, {p-[R(O)SnCH₂SiMe₂]₂C₆H₄}₃ (3) (R = (Me₃Si)₂CH), in which two six-membered Sn₃O₃ units are linked by three -CH₂Si(Me)₂C₆H₄Si(Me)₂CH₂- spacers.

Ring strain in boroxine rings: computational and experimental considerations

B3LYP/6-311+G(d) calculations indicate that (HBO)₃ (4) and (HBO)₄ (5) possess (zero-point energy corrected) strain enthalpies of 11.4 and 31.6 kJ mol⁻¹, respectively. The absence of eight-membered (RBO)₄ rings is attributed to a combination of ring strain and the lability of the B---O bond. The synthesis, characterization and molecular structure of (PhBO)₃·pyridine (1) are described and chemical phenomena related to the addition of amines to triorganoboroxine rings are rationalized in terms of relief of ring strain in 4.

Hexameric isopropyloxotin acetate chloroform tetrasolvate

The molecular structure of the centrosymmetric hexanuclear title compound, [ⁱPrSn(O)(O₂CCH₃)]₆·4CHCl1₃ or [Sn₆O₆(C₃H₇)₆(C₂H₃O₂)₆]·4CHCl₃, adopts the `drum' motif, in which two (ⁱPrSnO)₃ caps are linked via six ^μ₃-oxo atoms and six acetate groups. The Sn atoms are in distorted octahedral environments, defined by a CO₅ donor set for each of the three independent Sn atoms.

Observation of inter- and intramolecular C---H...F hydrogen bonding in Gingras' salt: [n-Bu4N]+[Ph3SnF2]-

The crystal and molecular structure of Gingras' salt [n-Bu₄N]^₊ [Ph₃SnF₂]⁻ is reported, which reveals a variety of inter- and intramolecular C---H...F hydrogen bonding interactions. A ¹¹⁹Sn MAS-NMR spectrum was recorded and a tensor analysis has been performed according to the method of Herzfeld and Berger. The results are discussed in terms of the molecular structure and are compared with the parent compound Ph₃SnF as well as with Mes₃SnF (Mes=mesityl).