Heterometallic cuboidal complexes as derivatives of the [MO3S4(H2O)9]4+ cluster

Heterometallic atoms can be incorporated into the Mo ₃ ^IV trinuclear ion [Mo₃S₄(H₂O)₉]⁴⁺ to give cuboidal complexes of the kind Mo₃MS₄, or related edge-linked species {Mo₃MS₄}₂, or corner-shared Mo₃S₄MS₄Mo₃ double cubes, depending on the heteroatom used. All of the products formed can be obtained as aqua ions. With four recent additions there are now 15 different heterometal atoms participating in this chemistry from Cr in Group 6 to Bi in Group 15. Preparative procedures, X-ray crystal structures, and distinctive properties including UV-Vis spectra, elution characteristics using Dowexcation exchange chromatography, ICP metal analyses, and the stoichiometries of reactions in which the heterometallic product is oxidized back to [Mo₃S₄(H₂O)₉]⁴⁺ (with release of the heterometal in an ionic form) are considered.Dedicated to Professor Jiaxi Lu on the occasion of his 80th birthday.     

Guided ion beam and theoretical study of the reactions of Au+ with H2, D2, and HD

Reactions of the late third-row transition metal cation Au(+) with H(2), D(2), and HD are examined using guided ion beam tandem mass spectrometry. A flow tube ion source produces Au(+) in its (1)S (5d(10)) electronic ground state level. Corresponding state-specific reaction cross sections for forming AuH(+) and AuD(+) as a function of kinetic energy are obtained and analyzed to give a 0 K bond dissociation energy of D(0)(Au(+)-H) = 2.13 ± 0.11 eV. Quantum chemical calculations at the B3LYP∕HW+∕6-311+G(3p) and B3LYP∕Def2TZVPP levels performed here show good agreement with the experimental bond energy. Theory also provides the electronic structures of these species and the reactive potential energy surfaces. We also compare this third-row transition metal system with previous results for analogous reactions of the first-row and second-row congeners, Cu(+) and Ag(+). We find that Au(+) has a stronger M(+)-H bond, which can be explained by the lanthanide contraction and relativistic effects that alter the relative size of the valence s and d orbitals. Results from reactions with HD provide insight into the reaction mechanism and indicate that ground state Au(+) reacts largely via a direct mechanism, in concordance with the behavior of the lighter group 11 metal ions, but includes more statistical behavior than these metals as well.     

Stereoselective total syntheses and reassignment of stereochemistry of the freshwater cyanobacterial hepatotoxins cylindrospermopsin and 7-epicylindrospermopsin

A stereoselective total synthesis of the structure 1 proposed for the freshwater cyanobacterial heptatotoxin cylindrospermopsin has been accomplished in approximately 30 operations starting from commercially available 4-methoxypyridine. Utilizing methodology developed by Comins, the tetrasubstituted piperidine A-ring unit of the hepatotoxin was efficiently constructed. The two remaining stereocenters in the natural product were then set by a stereospecific intramolecular N-sulfinylurea Diels-Alder cyclization/Grignard ring opening/allylic sulfoxide [2,3]-sigmatropic rearrangement sequence previously developed in these laboratories, leading to key intermediate 29. The stereochemical assignment of alcohol 29, which contains all six of the stereogenic centers of the natural product, was confirmed by an X-ray crystal structure determination of a derivative. Installation of the D-ring uracil moiety was effected by using our new methodology developed for this purpose, and construction of the C-ring guanidine completed the total synthesis of racemic structure 1. However, the (1)H NMR data for this compound do not match that of cylindrospermopsin, but instead agree with the data reported for 7-epicylindrospermopsin, a minor toxic metabolite that co-occurs with cylindrospermopsin. Therefore, we propose a revision of the stereochemical assignments of these natural products such that cylindrospermopsin is now represented as structure 2 and 7-epicylindrospermopsin is 1. This reassignment was further confirmed by Mitsunobu inversion of the C-7 alcohol 51 to epimer 52, and conversion of this compound to tetracyclic diol 57, which has previously been transformed to cylindrospermopsin (2).     

Metamorphosis of ordered mesopores to micropores: periodic silica with unprecedented loading of pendant reactive organic groups transforms to periodic microporous silica with tailorable pore size

Ordered porous silicas with unprecedented loadings of pendant vinyl groups have been synthesized via co-condensation of tetraethyl orthosilicate (TEOS) and triethoxyvinylsilane (TEVS) under basic conditions in the presence of cetyltrimethylammonium surfactant. The resulting organosilicate-surfactant composites exhibited at least one low-angle X-ray diffraction (XRD) peak up to the TEVS:TEOS molar ratio of 7:3 (70% TEVS loading) in the synthesis gel. The surfactant was removed from these composites without any structural collapse. Nitrogen adsorption provided strong evidence of the presence of uniformly sized pores and the lack of phase separation up to TEVS:TEOS ratios as high as 13:7 (65% TEVS loading), whereas (29)Si MAS NMR and high-resolution thermogravimetry showed essentially quantitative incorporation of the organosilane. Thus, a hitherto unachieved loading level for pendant groups, considered by many to be impossible to achieve for stable organosilicas because of the expected framework connectivity constraints, has been obtained. The resulting vinyl-functionalized silicas exhibited gradually decreasing pore diameter (from 2.8 to 1.7 nm for TEVS loadings of 25-65%) and pore volume as the loading of pendant groups increased, but the specific surface area was relatively constant. Because of the reactivity of vinyl groups, ordered silicas with very high loadings of these groups are expected to be robust starting materials for the synthesis of other organic-functionalized ordered microporous materials. Herein, we demonstrate that these starting materials can also be transformed via calcination into ordered microporous silicas with pore diameters tailorable from 2.5 to as little as 1.4 nm simply by using an appropriate loading of the vinyl-functionalized precursor. This ease of the micropore size adjustment and the attained degree of structural ordering (as judged from XRD) have not been reported before. The novel ordered microporous materials reported herein are promising as adsorbents and catalyst supports.     

Bond dissociation energies and radical stabilization energies associated with model peptide-backbone radicals

Bond dissociation energies (BDEs) and radical stabilization energies (RSEs) have been calculated for a series of models that represent a glycine-containing peptide-backbone. High-level methods that have been used include W1, CBS-QB3, U-CBS-QB3, and G3X(MP2)-RAD. Simpler methods used include MP2, B3-LYP, BMK, and MPWB1K in association with the 6-311+G(3df,2p) basis set. We find that the high-level methods produce BDEs and RSEs that are in good agreement with one another. Of the simpler methods, RBMK and RMPWB1K achieve good accuracy for BDEs and RSEs for all the species that were examined. For monosubstituted carbon-centered radicals, we find that the stabilizing effect (as measured by RSEs) of carbonyl substituents (CX=O) ranges from 24.7 to 36.9 kJ mol(-1), with the largest stabilization occurring for the CH=O group. Amino groups (NHY) also stabilize a monosubstituted alpha-carbon radical, with the calculated RSEs ranging from 44.5 to 49.5 kJ mol(-1), the largest stabilization occurring for the NH2 group. In combination, NHY and CX=O substituents on a disubstituted carbon-centered radical produce a large stabilizing effect ranging from 82.0 to 125.8 kJ mol(-1). This translates to a captodative (synergistic) stabilization of 12.8 to 39.4 kJ mol(-1). For monosubstituted nitrogen-centered radicals, we find that the stabilizing effect of methyl and related (CH2Z) substituents ranges from 25.9 to 31.7 kJ mol(-1), the largest stabilization occurring for the CH3 group. Carbonyl substituents (CX=O) destabilize a nitrogen-centered radical relative to the corresponding closed-shell molecule, with the calculated RSEs ranging from -30.8 to -22.3 kJ mol(-1), the largest destabilization occurring for the CH=O group. In combination, CH2Z and CX=O substituents at a nitrogen radical center produce a destabilizing effect ranging from -19.0 to -0.2 kJ mol(-1). This translates to an additional destabilization associated with disubstitution of -18.6 to -7.8 kJ mol(-1).     

A versatile chemo-enzymatic route to enantiomerically pure beta-branched alpha-amino acids

A series of diastereoisomers of beta-methyl-beta-phenylalanine analogues 1a-f have been prepared in enantiomerically pure form using a combination of chemo- and biocatalysis. Starting from l-threonine methyl ester 2, a range of beta,beta-disubstituted didehydroamino acids were obtained as their (Z)-isomers 6a-f. Asymmetric hydrogenation of these alkenes, using either the [Rh(R,R)-Et-DuPhos(COD)]BF4 or [Rh(S,S)-Et-DuPhos(COD)]BF4 catalyst, followed by hydrolysis yielded two of the four possible sets of diastereoisomers of the beta-branched amino acid. Subsequent stereoinversion, using a stereoselective amino acid oxidase in combination with a nonselective reducing agent, furnished the remaining two sets of diastereomers.     

Preprocessing of rotamers for protein design calculations

We have developed a process that significantly reduces the number of rotamers in computational protein design calculations. This process, which we call Vegas, results in dramatic computational performance increases when used with algorithms based on the dead-end elimination (DEE) theorem. Vegas estimates the energy of each rotamer at each position by fixing each rotamer in turn and utilizing various search algorithms to optimize the remaining positions. Algorithms used for this context specific optimization can include Monte Carlo, self-consistent mean field, and the evaluation of an expression that generates a lower bound energy for the fixed rotamer. Rotamers with energies above a user-defined cutoff value are eliminated. We found that using Vegas to preprocess rotamers significantly reduced the calculation time of subsequent DEE-based algorithms while retaining the global minimum energy conformation. For a full boundary design of a 51 amino acid fragment of engrailed homeodomain, the total calculation time was reduced by 12-fold.     

The Use of a Low‐Molar‐Mass Self‐Assembled Template to Direct the Crystallisation of Poly(ε‐caprolactone)

Summary: We show that small quantities of dibenzylidene sorbitol dispersed in poly(ε‐caprolactone) provide a self‐assembling nanoscale framework to yield high levels of crystal orientation. During modest shear flow of the melt, the additive forms highly extended nanoparticles which adopt a preferred alignment with respect to the flow field and, on cooling, polymer crystallisation is directed by these particles. We speculate that atomistic level epitaxy is unlikely to be the only directing influence.

SAXS pattern of PCL/DBS in the melt at 80 °C and subjected to a shear flow of 10 s⁻¹ for 1 000 shear units. The flow direction is vertical.     

Kuhn and the Chemical Revolution: a re-assessment

A recent paper by Hoyningen-Huene argues that the Chemical Revolution is an excellent example of the success of Kuhn’s theory. This paper gives a succinct account of some counter-arguments and briefly refers to some further existing counter-arguments. While Kuhn’s theory does have a small number of more or less successful elements, it has been widely recognised that in general Kuhn’s theory is a “preformed and relatively inflexible framework” (1962, p. 24) which does not fit particular historical examples well; this paper clarifies that those examples include the Chemical Revolution.