BINOL-3,3'-triflone N,N-dimethyl phosphoramidites: through-space 19F,31P spin-spin coupling with a remarkable dependency on temperature and solvent internal pressure

A combined computational and experimental study of the effects of solvent, temperature and stereochemistry on the magnitude of the through-space spin-spin coupling between 31P and 19F nuclei which are six-bonds apart is described. The reaction of 3-trifluoromethylsulfonyl-2,'2-dihydroxy-1,1'-binaphthalene (3-SO2CF3-BINOL) with hexamethylphosphorous triamide (P(NMe2)3) generates a pair of N,N-dimethylphosphoramidites which are diastereomeric due to their differing relative configurations at the stereogenic phosphorous centre and the axially chiral (atropisomeric) BINOL unit. Through-space NMR coupling of the 31P and 19F nuclei of the phosphoramidite and sulfone is detected in one diastereomer only. In the analogous N,N-dimethylphosphoramidite generated from 3,3'-(SO2CF3)2-BINOL only one of the diastereotopic trifluoromethylsulfone moieties couples with the 31P of the phosphoramidite. In both cases, the magnitude of the coupling is strongly modulated (up to 400 %) by solvent and temperature. A detailed DFT analysis of the response of the coupling to the orientation of the CF3 moiety with respect to the P-lone pair facilitates a confident assignment of the stereochemical identity of the pair of diastereomers. The analysis shows that the intriguing effects of environment on the magnitude of the coupling can be rationalised by a complex interplay of solvent internal pressure, molecular volume and thermal access to a wider conformational space. These phenomena suggest the possibility for the design of sensitive molecular probes for local environment that can be addressed via through-space NMR coupling.     

Tin-based organo-Zintl ions: alkylation and alkenylation of Sn9(4-)

Reactions of nine-atom deltahedral clusters (Zintl ions) of tin, Sn 9 (4-), with alkyl chlorides, RCl (R = (t) Bu, (n) Bu, (s) Bu), and alkynes (Me3Si-C[triple bond]C-SiMe3, Ph-C[triple bond]CH) yielded the corresponding alkylated and alkenylated clusters [Sn 9-R] (3-). The triple bonds of the alkynes are hydrogenated to double bonds in the process. These are the first tin-based organo-Zintl ions, that is Zintl ions of tin that were subsequently functionalized with organic groups. They are analogous to the recently reported germanium-based derivatives. The (t) Bu-, vinyl-, and styrene-functionalized clusters [Sn 9- (t) Bu] (3-), [Sn 9-CH=CH 2] (3-), and [Sn 9-CH=CH-Ph] (3-), respectively, were structurally characterized in the solid state with [K(2,2,2-crypt)] (+) countercations and in solution by electrospray mass spectrometry. Crystal data: [K(2,2,2-crypt)] 3[Sn 9- (t) Bu].2py, triclinic, P1, a = 14.4259(3), b = 16.2725(4), and c = 22.5593(5) A, alpha = 86.092(1), beta = 78.952(1), and gamma = 65.114(1) degrees , V = 4714.48(7) A (3), Z = 2; [K(2,2,2-crypt)] 3[Sn 9-CH=CH 2].2py, triclinic, P-1, a = 15.6988(3), b = 17.4195(4), and c = 17.4432(4) A, alpha = 86.299(1), beta = 81.566(1), and gamma = 85.349(1) degrees , V = 4696.27(18) A (3), Z = 2; [K(2,2,2-crypt)] 3[Sn 9-CH=CH-Ph].tol.0.75py, monoclinic, C2/c, a = 38.5883(9), b = 23.3893(5), and c = 25.0192(5) A, beta = 120.269(1) degrees , V = 19502.6(7) A (3), Z = 8.     

A high-field solid-state 35/37Cl NMR and quantum chemical investigation of the chlorine quadrupolar and chemical shift tensors in amino acid hydrochlorides

A series of six L-amino acid hydrochloride salts has been studied by 35/37Cl solid-state NMR spectroscopy (at 11.75 and 21.1 T) and complementary quantum chemical calculations. Analyses of NMR spectra acquired under static and magic-angle-spinning conditions for the six hydrochloride salts, those of aspartic acid, alanine, cysteine, histidine, methionine and threonine, allowed the extraction of information regarding the chlorine electric field gradient (EFG) and chemical shift tensors, including their relative orientation. Both tensors are found to be highly dependent on the local environment, with chlorine-35 quadrupolar coupling constants (CQ) ranging from -7.1 to 4.41 MHz and chemical shift tensor spans ranging from 60 to 100 ppm; the value of CQ for aspartic acid hydrochloride is the largest in magnitude observed to date for an organic hydrochloride salt. Quantum chemical calculations performed on cluster models of the chloride ion environment demonstrated agreement between experiment and theory, reproducing CQ to within 18%. In addition, the accuracy of the calculated values of the NMR parameters as a function of the quality of the input structure was explored. Selected X-ray structures were determined (L-Asp HCl; L-Thr HCl) or re-determined (L-Cys HCl.H2O) to demonstrate the benefits of having accurate crystal structures for calculations. The self-consistent charge field perturbation model was also employed and was found to improve the accuracy of calculated quadrupolar coupling constants, demonstrating the impact of the neighbouring ions on the EFG tensor of the central chloride ion. Taken together, the present work contributes to an improved understanding of the factors influencing 35/37Cl NMR interaction tensors in organic hydrochlorides.     

An inequality concerning the elasticity of Krull monoids with divisor class group $\mathbb{Z}_p$

Abstract  Let p be a prime integer and M a Krull monoid with divisor class group . We represent by S the set of nontrivial divisor classes of which contain prime divisors. We present a new inequality for the elasticity of M (denoted ρ (M)) which is dependent on the cardinality of S and argue that this inequality is the best possible. If M as above has | S| = 3, then it is known that , but for large p, not all the values in this containment set can be realized. For each | S| = 3, we produce a submonoid of such that

Elasticity in certain block monoids via the Euclidean table

This paper continues the study begun in [GEROLDINGER, A.: On non-unique factorizations into irreducible elements II, Colloq. Math. Soc. János Bolyai 51 (1987), 723–757] concerning factorization properties of block monoids of the form ℬ(ℤ _n , S) where S = (hereafter denoted ℬ _a (n)). We introduce in Section 2 the notion of a Euclidean table and show in Theorem 2.8 how it can be used to identify the irreducible elements of ℬ _a (n). In Section 3 we use the Euclidean table to compute the elasticity of ℬ _a (n) (Theorem 3.4). Section 4 considers the problem, for a fixed value of n, of computing the complete set of elasticities of the ℬ _a (n) monoids. When n = p is a prime integer, Proposition 4.12 computes the three smallest possible elasticities of the ℬ _a (p). Part of this work was completed while the second author was on an Academic Leave granted by the Trinity University Faculty Development Committee.     

Modified interfacial statistical associating fluid theory: a perturbation density functional theory for inhomogeneous complex fluids

A density functional theory based on Wertheim's first order perturbation theory is developed for inhomogeneous complex fluids. The theory is derived along similar lines as interfacial statistical associating fluid theory [S. Tripathi and W. G. Chapman, J. Chem. Phys. 122, 094506 (2005)]. However, the derivation is more general and applies broadly to a range of systems, retaining the simplicity of a segment density based theory. Furthermore, the theory gives the exact density profile for ideal chains in an external field. The general avail of the theory has been demonstrated by applying the theory to lipids near surfaces, lipid bilayers, and copolymer thin films. The theoretical results show excellent agreement with the results from molecular simulations.     

Water in oil emulsion droplet size characterization using a pulsed field gradient with diffusion editing (PFG-DE) NMR technique

This paper describes a proton nuclear magnetic resonance (NMR) technique, pulsed field gradient with diffusion editing (PFG-DE), to quantify drop size distributions of brine/crude oil emulsions. The drop size distributions obtained from this technique were compared to results from the traditional pulsed field gradient (PFG) technique. The PFG-DE technique provides both transverse relaxation (T2) and drop size distributions simultaneously. In addition, the PFG-DE technique does not assume a form of the drop size distribution. An algorithm for the selection of the optimal parameters to use in a PFG-DE measurement is described in this paper. The PFG-DE technique is shown to have the ability to resolve drop size distributions when the T2 distribution of the emulsified brine overlaps either the crude oil or the bulk brine T2 distribution. Finally, the PFG-DE technique is shown to have the ability to resolve a bimodal drop size distribution.     

Triaxial superdeformation in Lu

High-spin states in ¹⁶³Lu have been investigated using the Euroball spectrometer array. The previously known superdeformed band has been extended at low and high energies, and its connection to the normal-deformed states has been established. From its decay the mixing amplitude and interaction strength between superdeformed and normal states are derived. In addition, a new band with a similar dynamic moment of inertia has been found. The experimental results are compared to cranking calculations which suggest that the superdeformed bands in this mass region correspond to shapes with a pronounced triaxiality (γ≈±20°).     

Styrene and isoprene friction factors in styrene–isoprene matrices

Monomeric friction factors, Ξ, for polystyrene (PS), polyisoprene (PI), and a polystyrene–polyisoprene (SI) diblock copolymer have been determined as a function of temperature in four poly(styrene-b-isoprene-b-styrene-b-isoprene) tetrablock copolymer matrices. The Rouse model has been used to calculate the friction factors from tracer diffusion coefficients measured by forced Rayleigh scattering. Within the experimental temperature range the tetrablock copolymers are disordered, allowing for measurement of the diffusion coefficient in matrices with average compositions determined by the tetrablock copolymers (23, 42, 60, and 80% styrene by volume). Remarkably, for a given matrix composition the styrene and isoprene friction factors are essentially equivalent. Furthermore, at a constant interval from the system glass transition temperature, T_g, all of the friction factors (obtained from homopolymer, diblock copolymer, and tetrablock copolymer dynamics) agree to within an order of magnitude. This is in marked contrast to results for miscible polymer blends, where the individual components generally have distinct composition dependences and magnitudes at constant T − T_g. The homopolymer friction factors in the tetrablock matrices were systematically slightly higher than those of the diblock, which in turn were slightly higher than those of the homopolymers in their respective melts, when all compared at constant T − T_g. This is attributed to the local spatial distribution of styrene and isoprene segments in the tetrablocks, which presents a nonuniform free energy surface to the tracer molecules. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 3079–3086, 1998     

Theoretical Prediction and Explanation of Reaction Site Selectivity in the Addition of a Phenoxy Group to Perfluoropyrimidine,Perfluoropyridazine, and Perfluoropyrazine

Perfluoroaromatics, such as perfluoropyridine and perfluorobenzene, are privileged synthetic scaffolds in organofluorine methodology, undergoing a series of regioselective substitution reactions with a variety of nucleophiles. This unique chemical behavior allows for the synthesis of many perfluoroaromatic derived molecules with unique and diverse architectures. Recently, it has been demonstrated that perfluoropyridine and perfluorobenzene can be utilized as precursors for a variety of materials, ranging from high performance polyaryl ethers to promising drug scaffolds. In this work, using density functional theory, we investigate the possibility of perfluoropyrimidine, perfluoropyridazine, and perfluoropyrazine participating in similar substitution reactions. We have found that the first nucleophilic addition of a phenoxide group substitution on perfluoropyrimidine and on perfluoropyridazine would happen at a site para to one of the nitrogen atoms. While previous literature points to mesomeric effects as the primary cause of this phenomenon, our work demonstrates that this effect is enhanced by the fact that the transition states for these reactions result in bond angles that allow the phenoxide to π-complex with the electron-deficient diazine ring. The second substitution on perfluoropyrimidine and on perfluoropyridazine is most likely to happen at the site para to the other nitrogen. The second substitution on perfluoropyrazine is most likely to happen at the site para to the first substitution. The activation energies for these reactions are in line with those reported for perfluoropyridine and suggest that these platforms may also be worth investigation in the lab as possible monomers for high performance polymers.