Theoretical studies of atmospheric triatomic molecules: Ab initio characterization of Rydberg series in CO2

The ab initio Koopmans' Theorem is used to determine energy levels and orbital characteristics for the lowest members of s, p, d, f, g, h Rydberg series in CO₂. The energy levels are in good agreement with results of SCF calculations and experimental energy levels. It appears that unambiguous spectral assignments can be based upon the comparison of ab initio and observed energy levels in the case of penetrating Rydberg orbits. The energy levels associated with the higher angular momentum orbits exhibit degeneracies and separations which more closely approximate those of the hydrogen atom.     

Optical isotope shifts of146Sm and151Sm

We have measured the optical isotope shifts of¹⁴⁶Sm and¹⁵¹Sm by laser resonance fluorescence. From these measurements the changes in the mean square nuclear radii are: Δ〈r²〉 (A=144 to 146)=0.266(10) fm², and Δ〈r²〉 (A=151 to 152)=0.262(10) fm². These results, together with those of the stable isotopes, show that the average nuclear expansion of samarium can be accounted for by the liquid drop model with deformations.     

Continuous degeneracy and energy-localization of molecular orbitals

The energy-localization method is examined for continuous degeneracy using a grouptheoretic approach. Conditions for the degenerate orbitals are obtained and an enumeration of symmetry groups where continuous degeneracy may occur is given. It is found that the orbitals may be equivalent under operations not contained in the total symmetry group. An alternative explanation for the free rotation of the lone pairs in F₂ is offered.     

A Simple,Broad‐Scope Nickel(0) Precatalyst System for the Direct Amination of Allyl Alcohols

The preparation of allylic amines is traditionally accomplished by reactions of amines with reactive electrophiles, such as allylic halides, sulfonates, or oxyphosphonium species; such methods involve hazardous reagents, generate stoichiometric waste streams, and often suffer from side reactions (such as overalkylation). We report here the first broad‐scope nickel‐catalysed direct amination of allyl alcohols: An inexpensive Ni^II/Zn couple enables the allylation of primary, secondary, and electron‐deficient amines without the need for glove‐box techniques. Under mild conditions, primary and secondary aliphatic amines react smoothly with a range of allyl alcohols, giving secondary and tertiary amines efficiently. This “totally catalytic” method can also be applied to electron‐deficient nitrogen nucleophiles; the practicality of the process was demonstrated in an efficient, gram‐scale preparation of the calcium antagonist drug substance flunarizine (Sibelium®).     

A family of Mn16 single-molecule magnets from a reductive aggregation route

The synthesis and magnetic properties of three isostructural hexadecametallic manganese clusters [Mn(16)O(16)(OMe)(6)(O(2)CCH(2)Ph)(16)(MeOH)(6)] (1), [Mn(16)O(16)(OMe)(6)(O(2)CCH(2)Cl)(16)(MeOH)(6)] (2), and [Mn(16)O(16)(OMe)(6)(O(2)CCH(2)Br)(16)(MeOH)(6)] (3) are reported. The complexes were prepared by a reductive aggregation reaction involving phenylacetic acid, chloroacetic acid or bromoacetic acid, and NBu(n)()(4)MnO(4) in MeOH. Complex 1 crystallizes in the monoclinic space group C2/c and consists of 6 Mn(IV) and 10 Mn(III) ions held together by 14 mu(3)-O(2)(-), 2 mu-O(2)(-), 4 mu-MeO(-), and 2 mu-O(2)CCH(2)Ph(-) groups. The remaining 14 mu-O(2)CCH(2)Ph(-) ligands, 2 mu-MeO(-) groups, and 6 terminal MeOH molecules constitute the peripheral ligation in the complex. Variable-temperature, solid-state dc magnetic susceptibility measurements on 1-3 in the temperature range 5.0-300 K reveal that all three complexes are dominated by intramolecular antiferromagnetic exchange interactions. Low-lying excited states preclude an exact determination of the spin ground state for 1-3 by magnetization measurements. Alternating current susceptibility measurements at zero dc field in the temperature range 1.8-10 K and a 3.5 G ac field oscillating at frequencies in the 5-1488 Hz range display, at temperatures below 3 K, a nonzero, frequency-dependent chi(M)"signal for complexes 1-3, with the peak maxima lying at temperatures less than 1.8 K. Single-crystal magnetization versus dc field scans down to 0.04 K for complex 1 show hysteresis behavior at <1 K, establishing 1 as a new member of the SMM family. No clear steps characteristic of quantum tunneling of magnetization (QTM) were observed in the hysteresis loops.     

Studies on chelates of selected pyrazylmethyl ketones

Summary Several pyrazylmethyl ketones have been investigated in regard to their potential analytical utility as chelating agents for metal ions. Proton dissociation constants of the ligands and metal chelate formation constants were calculated from potentiometric data using the method of Irving and Rossotti. Chelate formation constants obtained in this study allow comparisons to be made between pyrazylmethyl ketones and other chelating agents possessing similar structures. The potential analytical utility of the title compounds is discussed.

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Zusammenfassung Einige Pyrazylmethylketone wurden auf ihre Fähigkeit zur Chelatbildung mit Metallionen untersucht. Die Protonendissoziationskonstanten der Liganden und die Chelatbildungskonstanten wurden aus potentiometrischen Daten berechnet, die nach Irving und Rossotti ermittelt wurden. Die Chelatbildungs-konstanten der Pyrazylmethylketone wurden mit denen ähnlich strukturierter Chelatbildner verglichen. Die analytische Brauchbarkeit der untersuchten Ketone wurde diskutiert.

     

Functional graft poly(N-isopropyl acrylamide)s using reversible addition-fragmentation chain transfer (RAFT) polymerisation

A series of NIPAM/4-vinyl benzyl chloride copolymers were substituted with 4(5)-imidazole dithioic acid or N-pyrrole dithioic acid to form multi-functional linear dithioate-functional polymers, which can be used as macromolecular transfer agents in a controlled radical polymerisation (RAFT) process. The presence of imidazole dithioate or N-pyrrole dithioate units along the NIPAM copolymer was determined by (1)H NMR, which showed broad CH-imidazole or CH-N-pyrrole resonances. Subsequent reaction of these multi-branch point polymers to produce graft polymers was achieved by reaction with NIPAM in the presence of AIBN. The graft polymers are produced as mixtures containing the desired product and linear polymer. The linear polymer is produced following transfer to the pendant dithioate group. Some of the branched polymers formed from the imidazole dithioate polymers were insoluble in water whilst others were found to be water soluble only in the presence of copper(II) ions. The use of N-pyrrole dithioate groups was found to substantially increase the solubility of the branched polymers in conventional solvents.     

Novel (n + 1 + 1) cycloaddition reactions; the formation of cyclic tetraphosphonium dications with four linked phosphorus atoms and an organic backbone

In the presence of SnCl(2), a novel cycloaddition of two moles of R'PCl(2) (R' = Et or Ph) to a diphosphane has been achieved, forming a cyclic dication with four linked phosphorus atoms and an organic backbone; two of these species have been characterised by single-crystal X-ray diffraction, and the mechanism of the reaction has been established.     

Chemical denaturants inhibit the onset of dewetting

The mechanism by which the aqueous cosolvents guanidinium chloride and urea denature proteins is a matter of controversy. Here, we use all-atom molecular dynamics simulations to study the effect of both denaturants on the dewetting of water confined between nanoseparated hydrophobic plates. It is found that the denaturants inhibit the onset of dewetting, so that it occurs at shorter interplate distances than in pure water. Our results support a role for urea and guanidinium in assisting in the solvation of nonpolar surfaces, thereby weakening hydrophobic effects known to be important for protein stability.     

General access to the vinca and tacaman alkaloids using a Rh(II)-catalyzed cyclization/cycloaddition cascade

The total synthesis of several members of the vinca and tacaman classes of indole alkaloids has been accomplished. The central step in the synthesis consists of an intramolecular [3+2]-cycloaddition reaction of an alpha-diazo indoloamide which delivers the pentacyclic skeleton of the natural product in excellent yield. The acid lability of the oxabicyclic structure was exploited to establish the trans-D/E ring fusion of (+/-)-3H-epivincamine (3). Finally, a base induced keto-amide ring contraction was utilized to generate the E-ring of the natural product. A variation of the cascade sequence of reactions used to synthesize (+/-)-3H-epivincamine was also employed for the synthesis of the tacaman alkaloids (+/-)-tacamonine and (+/-)-apotacamine.