Cationic Alkylaluminum-Complexed Zirconocene Hydrides: NMR-Spectroscopic Identification, Crystallographic Structure Determination, and Interconversion with Other Zirconocene Cations

The ansa-zirconocene complex rac-Me_2Si(1-indenyl)_2ZrCl_2 ((SBI)ZrCl_2) reacts with diisobutylaluminum hydride and trityl tetrakis(perfluorophenyl)borate in hydrocarbon solutions to give the cation [(SBI)Zr(μ-H)_3(Al^iBu_2)_2]^+, the identity of which is derived from NMR data and supported by a crystallographic structure determination. Analogous reactions proceed with many other zirconocene dichloride complexes. [(SBI)Zr(μ-H)_3(Al^iBu2)_2]^+ reacts reversibly with ClAl^iBu_2 to give the dichloro-bridged cation [(SBI)Zr(μ-Cl)_2Al^iBu_2]^+. Reaction with AlMe_3 first leads to mixed-alkyl species [(SBI)Zr(μ-H)_3(AlMe_x^iBu_(2−x))_2^]+ by exchange of alkyl groups between aluminum centers. At higher AlMe_3/Zr ratios, [(SBI)Zr(μ-Me)_2AlMe_2]^+, a constituent of methylalumoxane-activated catalyst systems, is formed in an equilibrium, in which the hydride cation [(SBI)Zr(μ-H)_3(AlR_2)_2]^+ strongly predominates at comparable HAl^iBu_2 and AlMe_3 concentrations, thus implicating the presence of this hydride cation in olefin polymerization catalyst systems

A Diphenylcyclopropene Complex of Tungsten, [WCl_2O(PMePh_2)_2(η^2-3,3-diphenylcyclopropene)], Precursor to a Tungsten–Oxo–Olefin Metathesis Catalyst

The title compound, dichlorobis(methyldiphenylphosphine-P) [(1,2-[η])-3,3-diphenylcyclopropene]oxotungsten, [WCl_2O(C_(15)H_(12))(C_(13)H_(13)P)_2], is a mononuclear complex of tungsten with an approximately octahedral environment around the metal atom. The ligand, 3,3-diphenylcyclopropene, is bonded to the W atom in a [η]^2-geometry with effectively identical metal-to-carbon bond distances [W-C1 = 2.133 (7) Å and W-C2 2.131 (7) Å]

IT-technology in the budgeting

Budgeting plays an important role in modern organization, it is the tool that is necessary for the survival of the company in a competitive environment. Budgeting has become necessary business management process, and like any management activities, it requires automation

Introducing willingness-to-pay for noise changes into transport appraisal: an application of benefit transfer.

Numerous research studies have elicited willingness-to-pay values for transport-related noise, however, in many industrialised countries including the UK, noise costs and benefits are still not incorporated into appraisals for most transport projects and policy changes (Odgaard et al, 2005; Grant-Muller et al, 2001). This paper describes the actions recently taken in the UK to address this issue, comprising: primary research based on the city of Birmingham; an international review of willingness-to-pay evidence; development of values using benefit transfers over time and locations; and integration with appraisal methods. Amongst the main findings are: that the willingness-to-pay estimates derived for the UK are broadly comparable with those used in appraisal elsewhere in Europe; that there is a case for a lower threshold at 1 45dB(A)Leq,18hr1 rather than the more conventional 55dB(A); and that values per dB(A) increase with the noise level above this threshold. There are significant issues over the valuation of rail versus road noise, the neglect of non-residential noise and the valuation of high noise levels in different countries. Conclusions are drawn regarding the feasibility of noise valuation based on benefit transfers in the UK and elsewhere, and future research needs in this field are discussed

The brightest pure-H ultracool white dwarf

We report the identification of LSR J0745+2627 in the United Kingdom InfraRed Telescope Infrared Deep Sky Survey (UKIDSS) Large Area Survey (LAS) as a cool white dwarf with kinematics and age compatible with the thick-disk/halo population. LSR J0745+2627 has a high proper motion (890 mas/yr) and a high reduced proper motion value in the J band (H_J=21.87). We show how the infrared-reduced proper motion diagram is useful for selecting a sample of cool white dwarfs with low contamination. LSR J0745+2627 is also detected in the Sloan Digital Sky Survey (SDSS) and the Wide-field Infrared Survey Explorer (WISE). We have spectroscopically confirmed this object as a cool white dwarf using X-Shooter on the Very Large Telescope. A detailed analysis of its spectral energy distribution reveals that its atmosphere is compatible with a pure-H composition model with an effective temperature of 3880+-90 K. This object is the brightest pure-H ultracool white dwarf (Teff<4000 K) ever identified. We have constrained the distance (24-45 pc), space velocities and age considering different surface gravities. The results obtained suggest that LSR J0745+2627 belongs to the thick-disk/halo population and is also one of the closest ultracool white dwarfs.Comment: 5 pages, 7 figures, accepted for publication in A&A Letter

Relativistic Effects in the Electromagnetic Current at GeV Energies

We employ a recent approach to the non-relativistic reduction of the electromagnetic current operator in calculations of electronuclear reactions. In contrast to the traditional scheme, where approximations are made for the transferred momentum, transferred energy and initial momentum of the struck nucleon in obtaining an on-shell inspired form for the current, we treat the problem exactly for the transferred energy and transferred momentum. We calculate response functions for the reaction $^2H(e,e'p)n$ at CEBAF (TJNAF) energies and find large relativistic corrections. We also show that in Plane Wave Impulse Approximation, it is always possible to use the full operator, and we present a comparison of such a limiting case with the results incorporating relativistic effects to the first order in the initial momentum of the struck nucleon.Comment: 31 pages, 8 figures, Revte

A Diphenylcyclopropene Complex of Tungsten, [WCl_2O(PMePh_2)_2(η^2-3,3-diphenylcyclopropene)], Precursor to a Tungsten–Oxo–Olefin Metathesis Catalyst

The title compound, dichlorobis(methyldiphenylphosphine-P) [(1,2-[η])-3,3-diphenylcyclopropene]oxotungsten, [WCl_2O(C_(15)H_(12))(C_(13)H_(13)P)_2], is a mononuclear complex of tungsten with an approximately octahedral environment around the metal atom. The ligand, 3,3-diphenylcyclopropene, is bonded to the W atom in a [η]^2-geometry with effectively identical metal-to-carbon bond distances [W-C1 = 2.133 (7) Å and W-C2 2.131 (7) Å]

NMR investigations of the interaction between the azo-dye sunset yellow and Fluorophenol

The interaction of small molecules with larger noncovalent assemblies is important across a wide range of disciplines. Here, we apply two complementary NMR spectroscopic methods to investigate the interaction of various fluorophenol isomers with sunset yellow. This latter molecule is known to form noncovalent aggregates in isotropic solution, and form liquid crystals at high concentrations. We utilize the unique fluorine-19 nucleus of the fluorophenol as a reporter of the interactions via changes in both the observed chemical shift and diffusion coefficients. The data are interpreted in terms of the indefinite self-association model and simple modifications for the incorporation of a second species into an assembly. A change in association mode is tentatively assigned whereby the fluorophenol binds end-on with the sunset yellow aggregates at low concentration and inserts into the stacks at higher concentrations