Steric and electronic properties of N-heterocyclic carbenes (NHC): a detailed study on their interaction with Ni(CO)4

N-heterocyclic carbene ligands IMes (1), SIMes (2), IPr (3), SIPr (4), and ICy (5) react with Ni(CO)(4) to give the saturated tricarbonyl complexes Ni(CO)(3)(IMes) (8), Ni(CO)(3)(SIMes) (9), Ni(CO)(3)(IPr) (10), Ni(CO)(3)(SIPr) (11), and Ni(CO)(3)(ICy) (12), respectively. The electronic properties of these complexes have been compared to their phosphine analogues of general formula Ni(CO)(3)(PR(3)) by recording their nu(CO) stretching frequencies. While all of these NHCs are better donors than tertiary phosphines, the differences in donor properties between ligands 1-5 are surprisingly small. Novel, unsaturated Ni(CO)(2)(IAd) (13) and Ni(CO)(2)(I(t)()Bu) (14) compounds are obtained from the reaction of Ni(CO)(4) with IAd (6) and I(t)()Bu (7). Complexes 13 and 14 are highly active toward substitution of the NHC as well as the carbonyl ligands. This has allowed the determination of Ni-C(NHC) bond dissociation energies and the synthesis of various unsaturated Ni(0) and Ni(II) complexes. Computational studies on compounds 8-14 are in line with the experimental findings and show that IAd (6) and I(t)()Bu (7) are more bulky than IMes (1), SIMes (2), IPr (3), SIPr (4), and ICy (5). Furthermore, a method based on %V(bur) values has been developed for the direct comparison of steric requirements of NHCs and tertiary phosphines. Complexes 8-14, as well as NiCl(C(3)H(5))(I(t)()Bu) (16) and NiBr(C(3)H(5))(I(t)()Bu) (17), have been characterized by X-ray crystallography.     

Influenza neuraminidase inhibitors possessing a novel hydrophobic interaction in the enzyme active site: design, synthesis, and structural analysis of carbocyclic sialic acid analogues with potent anti-influenza activity

The design, synthesis, and in vitro evaluation of the novel carbocycles as transition-state-based inhibitors of influenza neuraminidase (NA) are described. The double bond position in the carbocyclic analogues plays an important role in NA inhibition as demonstrated by the antiviral activity of 8 (IC50 = 6.3 microM) vs 9 (IC50 > 200 microM). Structure-activity studies of a series of carbocyclic analogues 6a-i identified the 3-pentyloxy moiety as an apparent optimal group at the C3 position with an IC50 value of 1 nM for NA inhibition. The X-ray crystallographic structure of 6h bound to NA revealed the presence of a large hydrophobic pocket in the region corresponding to the glycerol subsite of sialic acid. The high antiviral potency observed for 6h appears to be attributed to a highly favorable hydrophobic interaction in this pocket. The practical synthesis of 6 starting from (-)-quinic acid is also described.     

Reactivity of a N-heterocyclic carbene, 1,3-di-(1-adamantyl) imidazol-2-ylidene, with a pseudo-acid: structural characterization of Claisen condensation adduct

The reactivity of a N-heterocyclic carbene (NHC) with a pseudo-acid (ester in this case) is described. The product results from an unusual C-H bond activation. The structure of the product has been established by a single crystal diffraction study.     

Stabilisation of emulsions using hydrophobically modified inulin (polyfructose)

Oil-in-water (O/W) emulsions were prepared using a hydrophobically modified inulin surfactant, INUTEC^®SP1. The quality of the emulsions was evaluated using optical microscopy. Emulsions, prepared using INUTEC^®SP1 alone had large droplets, but this could be significantly reduced by addition of a cosurfactant to the oil phase, namely Span 20. The stability of the emulsions was investigated in water, in 0.5, 1.0 and 2 mol dm⁻³ NaCl as well as 0.5, 1.0, 1.5 and 2 mol dm⁻³ MgSO₄. All emulsions containing NaCl did not show any strong flocculation or coalescence up to 50 °C for almost 1 year storage. With MgSO₄ they were stable up to 50 °C and 1 mol dm⁻³. The stability of the emulsions against strong flocculation and coalescence could be attributed to the conformation of the polymeric surfactant at the O/W interface (multipoint attachment with several loops) and the strong hydration of the polyfructose chain in such high electrolyte concentrations. This was confirmed using cloud point measurements, which showed absence of any cloudiness up to 100 °C and at NaCl concentrations reaching 4 mol dm⁻³ and MgSO₄ reaching 1 mol dm⁻³. These high cloud points in electrolyte solutions could not be reached with polyethylene glycol. This clearly demonstrated the superiority of INUTEC^®SP1 surfactant as an emulsion stabiliser when compared with surfactants based on polyethylene glycol. Viscoelastic measurements showed a gradual increase in the storage modulus G′ with storage time both at room temperature and 50 °C. This was indicative of weak flocculation and absence of coalescence. The weak flocculation of the emulsions could be attributed to the presence of an energy minimum, G_min, in the energy–distance curve.     

A theoretical investigation of the origins of the green and red spectra of Ca2

The potential energy curves and transition moments of the ground state of Ca₂ and ¹Σ⁺_u states correlating with the ¹S + ¹P and ¹S + ¹D calcium atoms have been calculated. The calculations support the assignment of the observed emission spectra of Ca₂ in the red and in the green to transitions between the ground state and the 1,2¹Σ⁺_u states. Predissociation of the 1¹Σ⁺_u state is also shown to be possible from an interaction with the 1³Π_u state.     

Electronic states of Al2

Ab initio multi-configuration self-consistent field and first-order configuration interaction (FOCI) calculations in an extended basis set have been carried out for the lower energy electronic states of Al₂. The ten core electrons of each Al atom were replaced by an accurate compact effective core potential. The FOCI calculated T_o value for the ³Σ_g^?-³Σ_u^? transition agrees with the experimentally observed emission band to within 90 cm^?1. ³Π_u is calculated to be the electronic ground state of Al₂. Based on FOCI energies and qualitative intensity arguments, the reported optical absorption spectrum of matrix isolated Al₂ also agrees best with a ³Π_u ground state. The ³Σ_g^?1 state is calculated (T_e) at only 324 cm^?1 above the ³Π_u state, and the ¹ΣE_g⁺ state is predicted to lie higher.     

Synthetic control leading to chiral compounds

A highly diastereoselective cross aldol reaction is developed using divalent tin enolates formed from stannous trifluoromethanesulfonate and carbonyl compounds. The reaction is extended to a highly enantioselective cross aldol reaction employing chiral diamines derived from (S)-proline as ligands.     

pH-DEPENDENCE OF RHODAMINE B SEMIQUINONE DISMUTATION RATE IN AQUEOUS ALCOHOLIC SOLUTION

Abstract— A single transient species is observed in absorption following the flash irradiation of dilute deoxygenated aqueous alcoholic solutions of rhodamine B in hte pH range 5.5–7.0 The second-order decay constant for this semiquinone radical is an approximate linear function of the prevailing hydrogen ion concentration, the transient persisting for a period of from several seconds in neutral solution to several hours at pH = 12.
The slow rate of decay and its pH-dependence are explained in terms of an electron or H-atom transfer between the (unobserved) protonated and (observed) unprotonated semiquinone radical with simultaneous regeneration of hte D^+> and production of the leuco-dye DH:—
D·+ DH·⁺→ D⁺+ DH
Insofar as the reactant concentrations are controlled by the acid dissociation constant K^a of DH^.+ the data are consistent with a value of 5.5±1.0 for pK_a and a pH-independent rate constant K_o of 1.3±0.5×10⁶ 1. Mole^-1 sec^-1 at 20C.     

Pairing correlations: I. The ground-state coupled-cluster formalism as a unifying approach

the general problem of pairing correlations within a many-fermion system of identical particles is discussed at some length. We show in this first work in a series how the ground-state version of the [exp(S) or] coupled-cluster formalism (CCF) of quantum many-body theory may be rather generally applied to this problem, and how it thereby provides a very powerful and unifying approach to it. At the so-called SUB2 level of truncation, which is the lowest natural level of approximation for homogeneous systems, the CCF may be cast as a nonlinear integral equation for a four-point correlation function,S ₂, which provides a measure of the two-particle/two-hole component in the true ground-state wavefunction. This approximation couples the particle-particle, hole-hole and particle-hole correlations simultaneously, and treats them all on an equal footing. In the present work we concentrate particular attention on particle-particle and hole-hole correlations by focussing on the formulation of generalised ladder approximations within the CCF. These are therefore likely to be physically applicable in the low-density regime. In particular, we show that the well-known Galitskii approximation may be formulated within the CCF as that drastic sub-approximation to the full SUB2 equation which keeps only the so-called complete ladder (CLAD) terms, which we describe. A second paper applies the CCF to the particular case of a general (non-local) separable potential, and obtains exact analytic solutions within the CLAD approximation for the corresponding wavefunctions of the simultaneous particle-particle and hole-hole substructures within the many-fermion system.     

Pairing correlations: II. Exact model ground-state results for generalised ladders

In this series of papers, the so-called ground-state version of the [exp(S) or] coupled-cluster formalism (CCF) of quantum many-body theory is applied to the general problem of pairing correlations within a many-body system of identical fermions. In this second work in the series we restrict ourselves to exact calculations and concentrate on analytic solutions to the generalised ladder approximations formulated in the first paper. We focus attention on the particular model case of a general (non-local) separable potential, and work within the so-called complete ladder (CLAD) approximation which was shown in the earlier paper to be the CCF formulation of the well-known Galitskii approximation. We show how the CLAD approximation reduces in this case to a highly non-trivial pair of coupled nonlinear integral equations for the four-point correlation function,S ₂, which provides a measure of the two-particle/two-hole component in the true ground-state wave-function. In the further derivation of exact analytic solutions for bothS ₂ and the corresponding ground-state energy, we also see how various types of composite pairs within the many-body medium manifest themselves as virtual (de-)excitations. We thus show how our CCF provides an efficient and unified framework in which to describe all aspects of pairing, such as: (i) a possible free bound pair and its gradual approach to dissolution as the density is increased; (ii) the possible appearance of a second bound pair of predominantly hole-like quasi-particles above some lower critical density (which depends on the total momentum of the pair); (iii) the unstable but bound resonant pairs that can exist for densities above a comparable upper critical density at which the two previous types of real bound pairs have dissolved; and (iv) Cooper pairs. Even though each of these composite pairs leads to a new condensed-pair phase of lower energy, we further show that our so-called ground-state CCF leads only to the fluid-like state of uncondensed particles. In a third paper in this series we use the solutions obtained here as input to the analogous excited-state version of the CCF, and show how these various composite pairs materialise as negative energy (de-)excitations.