]Preparation and x-ray crystal structure of biss(diphenylphosphino)methanido platinum(II), [Pt(Ph2PCHPPh2)2]

[Pt(Ph₂PCHPPh₂)₂], the first homoleptic complex containing the chelated bis(diphenylphosphino)methanide ligand, has been synthesised by reaction of K₂[PtCl₄] and Ph₂PCH₂PPh₂ with KOH in ethanol, and characterised by ¹H and ³¹P NMR spectroscopy and X-ray crystallography.     

Organothiometallate - alkyne addition products. The crystal and molecular structure of [(η5-C5H5)W{C(CO2Me)C(CO2Me)C(O)SMe} (CO)2]

The title compound is the final product of the reaction between dimethylacetylene dicarboxylate and [(η⁵-C₅H₅)W(SMe) (CO)₃ ]. Its molecular structure has been established by an $\text{x}$-ray analysis based on 3301 diffractometric intensities. The crystals are monoclinic, space group $\text{P}$2₁/$\text{a}$, with four molecules in a cell of dimensions $\text{a}$ = 10.323(2), $\text{b}$ = 16.016(2), $\text{c}$ = 10.437(2)», β = 103.56(2)°. After least-squares refinement $\text{R}$ = 0.036. The tungsten co-ordination is square-pyramidal, the apical site being occupied by the centroid of the cyclopentadienyl ring. The basal co-ordination sites contain two carbonyl groups and also the sulphur and σ-bonded carbon atoms of a chelating carbothiolic methyl ester ligand derived from the incoming alkyne and CO and SMe groups of the original complex. The W-S and σ-W-C bond lengths are 2.440(2) and 2.194(7)».     

Divergent synthesis of two novel muscarine analogues from D-glucose

A divergent synthesis of two new muscarine analogues bearing the (5S)-dioxolanyl isosteric group was achieved starting from d-glucose, enabling access to libraries of potential muscarinic agonists or antagonists. The key step of the synthesis involved a regioselective epoxide ring opening in 2,5:3,4-dianhydro derivatives 5 and 15 with LiAlH₄, whereby the natural stereochemistry of (+)-muscarine (1) and (−)-allo-muscarine (2) was efficiently established.     

Oxidative addition with methyl group transfer in Diplatinum complexes: Crystal structure of a bridged platinum(IV)-platinum(II) complex

Reactions of [Me₂Pt(μ-dmpm)₂PtMe₂], (dmpm = Me₂PCH₂PMe₂) with halogens, (X₂) or methyl iodide give the platinum(IV)-platinum(II) complexes [Me₃Pt(μ-X)(μ-dmpm)₂PtMe]X or [Me₃IPt(μ-dmpm)₂PtMe₂] respectively, and the former reactions involve methyl group transfer between the platinum atoms of the binuclear complex; one of the derivatives ([Me₃Pt(μ-I)(μ-dmpm)₂PtL]I₃, L = 1/2I + 1/2 Me) is characterized by an X-ray crystal structure determination.     

On Equitorsion Holomorphically Projective Mappings of Generalized Kählerian Spaces

In this paper we investigate holomorphically projective mappings of generalized Kählerian spaces. In the case of equitorsion holomorphically projective mappings of generalized Kählerian spaces we obtain five invariant geometric objects for these mappings.     

Scaling Transform and Stretched States in Quantum Mechanics

We consider the Husimi Q(q, p)-functions which are quantum quasiprobability distributions on the phase space. It is known that, under a scaling transform (q; p) → (?q; ?p), the Husimi function of any physical state is converted into a function which is also the Husimi function of some physical state. More precisely, it has been proved that, if Q(q, p) is the Husimi function, the function ?² Q(?q; ?p) is also the Husimi function. We call a state with the Husimi function ?² Q(?q; ?p) the stretched state and investigate the properties of the stretched Fock states. These states can be obtained as a result of applying the scaling transform to the Fock states of the harmonic oscillator. The harmonic-oscillator Fock states are pure states, but the stretched Fock states are mixed states. We find the density matrices of stretched Fock states in an explicit form. Their structure can be described with the help of negative binomial distributions. We present the graphs of distributions of negative binomial coefficients for different stretched Fock states and show the von Neumann entropy of the simplest stretched Fock state.     

Treatment of the multimode Jahn-Teller problem in small aromatic radicals

The family of the Jahn-Teller (JT) active hydrocarbon rings, C(n)H(n) (n = 5-7), was analyzed by the means of multideterminantal density functional theory (DFT) approach. The multimode problem was addressed using the intrinsic distortion path (IDP) method, in which the JT distortion is expressed as a linear combination of all totally symmetric normal modes in the low symmetry minimum energy conformation. Partitioning of the stabilization energy into the various physically meaningful terms arising from Kohn-Sham DFT has been performed to get further chemical insight into the coupling of the nuclear movements and the electron distribution.     

High-resolution mass spectrometry and hydrogen/deuterium exchange study of mitorubrin azaphilones and nitrogenized analogues

Azaphilones represent numerous groups of wild fungal secondary metabolites that exhibit exceptional tendency to bind to nitrogen atoms in various molecules, especially those containing the amine group. Nitrogenized analogues of mitorubrin azaphilones, natural secondary metabolites of Hypoxylon fragiforme fungus, have been detected in the fungal methanol extract in very low concentrations. Positive electrospray ionization interfaced with high-resolution mass spectrometry was applied for confirmation of the elemental composition of protonated species. Collision-induced dissociation (CID) experiments have been performed, and fragmentation mechanisms have been proposed. Additional information regarding both secondary metabolite analogue families has been reached by application of gas-phase proton/deuterium (H/D) exchanges performed in the collision cell of a triple quadrupole mass spectrometer. An incomplete H/D exchange with one proton less than expected was observed for both protonated mitorubrin azaphilones and their nitrogenized analogues. By means of the density functional theory, an appropriate explanation of this behavior was provided, and it revealed some information concerning gas-phase H/D exchange mechanism and protonation sites. Copyright ? 2012 John Wiley & Sons, Ltd.