η1-Allylpalladium complexes with a tridentate PNP ligand with different phosphino groups

The iminodiphosphine 2-(PPh2)C6H4-1-CHvNC6H4-2-(PPh2) (P–N–P′) is used for the preparation of the complexes [Pd(η1-CHR1–CHvCR2R3)(P–N–P′)]BF4 [R1 = R2 = R3 = H: (1); R1 = R2 = Ph, R3 = H: (2); R1 = R3 = H, R2 = Ph: (3); R1 = H, R2 = R3 = Me: (4)]. The P–N–P′ tridentate coordination and the η1-allyl bonding mode in the solid are confirmed by the X-ray structural analysis of 1. In solution, the complexes 1 and 2 undergo an η1–η3–η1 rearrangement at 298 K interconverting the bonding site of the allyl group. A five-coordinate structure with the phosphine ligands in the axial position is proposed for the η3-allyl intermediate. For the dynamic process, a ΔG≠ value of 53.8 kJ mol−1 is obtained from 1H NMR data of 2. In 3 and 4, the allyl ligand is rigidly bound to the metal through the less substituted terminus, in line with the higher free energy content of the corresponding isomers: [Pd(η1-CHPh– CHvCH2)(P–N–P′)]+ +48.78 kJ mol−1; [Pd(η1-CMe2–CHvCH2)(P–N–P′)]+ +69.35 kJ mol−1. The complexes react with secondary amines in the presence of fumaronitrile at different rates yielding allylamines and the palladium(0) derivative [Pd(η2-fn)(P–N–P′)] (5). On the basis of charge distribution on the allylic carbon atoms and of steric factors, the difference in rate and the regioselectivity in the amination of 1–3 are better rationalized by a mechanism with nucleophilic attack at the η3-intermediate rather than by an SN2 mechanism with nucleophilic attack at the Pd–CHR1 carbon atom. The high regioselectivity in the reaction of 4 with piperidine implies an SN2′ mechanism with nucleophilic attack at the CMe2 allyl carbon. A dynamic process occurs also for the 18-electron complex 5 consisting in a dissociation–association equilibrium of the olefin

[PdCl2{8-(di-tert-butylphosphinooxy)quinoline)}]: a highly efficient catalyst for Suzuki-Miyaura reaction

The complex [PdCl2(P-N)] containing the basic and sterically demanding 8-(di-tert-butylphosphinooxy)quinoline ligand (P-N) is a highly efficient catalyst for the coupling of phenylboronic acid with aryl bromides or aryl chlorides. The influence of solvent and base has been investigated, the highest rates being observed at 110 C in toluene with K2CO3 as the base. With aryl bromides the reaction rates are almost independent on the electronic properties of the para aryl substituents, on the contrary, reduced reaction rates are observed when bulky substituents are present on the substrate. Nevertheless the coupling of 2-bromo-1,3,5-trimethylbenzene with phenylboronic acid can be carried out to completion in 2 h using a catalyst loading of 0.02 mol %. Under optimized reaction conditions, turnover frequencies as high as 1900 h(-1) can be obtained in the coupling of 4-chloroacetophenone with phenylboronic acid: lower reaction rates are obtained with Substrates bearing EDG substituents on the aryl group. (C) 2009 Elsevier Ltd. All rights reserved

The effects of primordial non-Gaussianity on the cosmological reionization

We investigate the effects of non-Gaussianity in the primordial density field on the reionization history. We rely on a semi-analytic method to describe the processes acting on the intergalactic medium (IGM), relating the distribution of the ionizing sources to that of dark matter haloes. Extending previous work in the literature, we consider models in which the primordial non-Gaussianity is measured by the dimensionless non-linearity parameter f_NL, using the constraints recently obtained from cosmic microwave background data. We predict the ionized fraction and the optical depth at different cosmological epochs assuming two different kinds of non-Gaussianity, characterized by a scale-independent and a scale-dependent f_NL and comparing the results to those for the standard Gaussian scenario. We find that a positive f_NL enhances the formation of high-mass haloes at early epochs, when reionization begins, and, as a consequence, the IGM ionized fraction can grow by a factor up to 5 with respect to the corresponding Gaussian model. The increase of the filling factor has a small impact on the reionization optical depth and is of order ~ 10 per cent if a scale-dependent non-Gaussianity is assumed. Our predictions for non-Gaussian models are in agreement with the latest WMAP results within the error bars, but a higher precision is required to constrain the scale dependence of non-Gaussianity.Comment: 10 pages, 8 figures, minor changes to match the version accepted for publication by MNRA

Mechanistic understanding of chromium-based oligomerisation catalysts : an EPR and ENDOR investigation

Electron Paramagnetic Resonance (EPR) and Electron Nuclear Double Resonance (ENDOR) spectroscopies have been used to study the fundamental nature of chromium-based selective oligomerisation catalysts. A series of 'pre-catalyst' complexes were fully characterised CW-EPR revealed each complex to possess an axial g matrix (g > ge > g ) and superhyperfine coupling to two equivalent 31P nuclei, consistent with a low-spin cf species of approximate Cjv symmetry, where the metal contribution to the SOMO is primarily dxy. The isotropic component to the 31P coupling was of a larger magnitude in those Cr(I) complexes bearing PNP ligands than those bearing PCP, indicating that the phosphorus 3s character in the SOMO was higher for the former. CW-ENDOR demonstrated that subtle structural differences in the complexes, namely in the phenyl ring conformations, occurred as a function of ligand type. Pulsed experiments proved that the technique is valid and viable for further work on the activated system. Upon activation of the pre-catalyst with an alkylaluminium, four distinct paramagnetic centres were identified. A Cr(I) bis-arene complex was firstly detected it was found to form either via intramolecular co-ordination of the ligand phenyl groups, or preferentially via solvent-based arene co-ordination, if such groups were available. Two further species (I and III) were subsequently observed at low temperatures the spin Hamiltonian parameters extracted for both showed that a significant modification to the structure of the pre-catalyst had occurred. Half-field transitions indicated the possibility of a dimeric nature to Species III. ENDOR measurements detected an exceptionally large proton coupling in the activated system, possibly due to the co ordination of alkyl fragments to the metal centre. A final, fourth paramagnetic centre (Species IV), was detected and classed as an intermediate species, due to the greater similarity between its g and A matrices with those of the parent complex, than the other activated species. Finally, a preliminary investigation into analogous pre-catalyst complexes bearing N-heterocyclic carbene ligands was performed, due to their similar employment in oligomerisation catalysis CW-EPR spectra revealed information on both their electronic and structural natures.EThOS - Electronic Theses Online ServiceGBUnited Kingdo

Kinetic Studies of the Oxidative Addition and Transmetallation Steps Involved in the Cross-Coupling of Alkynyl Stannanes with Aryl Iodides Catalysed by teta2-(Dimethyl fumarate)(iminophosphane)palladium(0) Complexes

The complexes [Pd(eta(2)-dmfu)(P-N)] {dmfu = dimethyl fumarate; P-N = 2-(PPh2)C6H4-1-CH=NR, R = C6H4OMe-4 (1a), CHMe2 (2a), C6H3Me2-2,6 (3a), C6H3(CHMe2)(2)-2,6 (4a)} undergo dynamic processes in solution which consist of a P-N ligand site exchange through initial rupture of the Pd-N bond at lower energy and an olefin dissociation-association at higher energy. According to equilibrium constant values for olefin replacement, the complex [Pd(eta(2)-fn)(P-N)] (fn = fumaronitrile, 1b) has a greater thermodynamic stability than its dmfu analogue 1a. The kinetics of the oxidative addition of ArI (Ar = C6H4CF3-4) to 1a and 2a lead to the products [PdI(Ar)(P-N)] (1c, 2c) and obey the rate law, k(obs) = k(1A) + k(2A)[ArI]. The k(1A) step involves oxidative addition to a reactive species [Pd(solvent)(P-N)] formed from dmfu dissociation. The k2A step is better interpreted in terms of oxidative addition to a species [Pd(eta(2) -dmfu) (solvent) (kappa(1)-P-N)] formed in a pre-equilibrium step from Pd-N bond breaking. The complexes 1c and 2c react with PhCequivalent toCSnBu(3) in the presence of an activated olefin (ol = dmfu, fn) to yield the palladium(0) derivatives [Pd(eta(2)-ol)(P-N)] along with lSnBu(3) and PhCequivalent toCAr. The kinetics of the transmetallation step, which is rate-determining for the overall reaction, obey the rate law: k(obs) = k(2T)[PhCequivalent toCSnBu(3)]. The k(2T) values are markedly enhanced in more polar solvents such as CH3CN and DMF. The solvent effect and the activation parameters suggest an associative S(E)2 mechanism with substantial charge separation in the transition state. The kinetic data of the above reactions in various solvents indicate that, for the cross-coupling of PhCequivalent toCSnBu(3) with ArI catalysed by 1a or 2a, the rate-determining step is represented by the oxidative addition and that CH3CN is the solvent in which the highest rates are observed. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004

HERG potassium channels are constitutively expressed in primary human acute myeloid leukemias and regulate cell proliferation of normal and leukemic hemopoietic progenitors

An important target in the understanding of the pathogenesis of acute myeloid leukemias (AML) relies on deciphering the molecular features of normal and leukemic hemopoietic progenitors. In particular, the analysis of the mechanisms involved in the regulation of cell proliferation is decisive for the establishment of new targeted therapies. To gain further insight into this topic we report herein a novel approach by analyzing the role of HERG K+ channels in the regulation of hemopoietic cell proliferation. These channels, encoded by the human ether-a-go-go-related gene (herg), belong to a family of K, channels, whose role in oncogenesis has been recently demonstrated. We report here that herg is switched off in normal peripheral blood mononuclear cells (PBMNC) as well as in circulating CD34(+) cells, however, it is rapidly turned on in the latter upon induction of the mitotic cycle. Moreover, herg appears to be constitutively activated in leukemic cell lines as well as in the majority of circulating blasts from primary AML. Evidence is also provided that HERG channel activity regulates cell proliferation in stimulated CD34(+) as well as in blast cells from AML patients. These results open new perspectives on the pathogenetic role of HERG K+ channels in leukemias