Radical anionic versus neutral 2,2′-bipyridyl coordination in uranium complexes supported by amide and ketimide ligands

The synthesis and characterization of (bipy)₂U(N[t-Bu]Ar)₂ (1-(bipy)₂, bipy = 2,2′-bipyridyl, Ar = 3,5-C₆H₃Me₂), (bipy)U(N[1Ad]Ar)₃ (2-bipy), (bipy)₂U(NC[t-Bu]Mes)₃ (3-(bipy)2, Mes = 2,4,6-C₆H₂Me₃), and IU(bipy)(NC[t-Bu]Mes)₃ (3-I-bipy) are reported. X-ray crystallography studies indicate that bipy coordinates as a radical anion in 1-(bipy)₂ and 2-bipy, and as a neutral ligand in 3-I-bipy. In 3-(bipy)₂, one of the bipy ligands is best viewed as a radical anion, the other as a neutral ligand. The electronic structure assignments are supported by NMR spectroscopy studies of exchange experiments with 4,4′-dimethyl-2,2′-bipyridyl and also by optical spectroscopy. In all complexes, uranium was assigned a +4 formal oxidation state.National Science Foundation (U.S.) (Grant CHE-9988806

Massless D-Branes on Calabi-Yau Threefolds and Monodromy

We analyze the link between the occurrence of massless B-type D-branes for specific values of moduli and monodromy around such points in the moduli space. This allows us to propose a classification of all massless B-type D-branes at any point in the moduli space of Calabi-Yau's. This classification then justifies a previous conjecture due to Horja for the general form of monodromy. Our analysis is based on using monodromies around points in moduli space where a single D-brane becomes massless to generate monodromies around points where an infinite number become massless. We discuss the various possibilities within the classification.Comment: 29 pages, LaTeX2e, 3 figures, author order fixe

Preparation of multiblock copolymers via step-wise addition of l-lactide and trimethylene carbonate.

Poly(l-lactide) (PLA) is a bioderived and biodegradable polymer that has limited applications due to its hard and brittle nature. Incorporation of 1,3-trimethylene carbonate into PLA, in a block copolymer fashion, improves the mechanical properties, while retaining the biodegradability of the polymer, and broadens its range of applications. However, the preparation of 1,3-trimethylene carbonate (TMC)/l-lactide (LA) copolymers beyond diblock and triblock structures has not been reported, with explanations focusing mostly on thermodynamic reasons that impede the copolymerization of TMC after lactide. We discuss the preparation of multiblock copolymers via the ring opening polymerization (ROP) of LA and TMC, in a step-wise addition, by a ferrocene-chelating heteroscorpionate zinc complex, {[fc(PPh2)(BH[(3,5-Me)2pz]2)]Zn(μ-OCH2Ph)}2 ([(fcP,B)Zn(μ-OCH2Ph)]2, fc = 1,1'-ferrocenediyl, pz = pyrazole). The synthesis of up to pentablock copolymers, from various combinations of LA and TMC, was accomplished and the physical, thermal, and mechanical properties of the resulting copolymers evaluated

An Unusual Hydrogen Migration/C−H Activation Reaction with Group 3 Metals

A novel hydrogen migration from the phenyl ring to the pyridine ring of an yttrium pyridyl complex supported by a 1,1′-ferrocene diamide ligand is reported. Density functional theory calculations were instrumental in probing the mechanism for this transformation

Reaction of Group III Biheterocyclic Complexes

Group III alkyl complexes supported by a ferrocene diamide ligand (1,1′-fc(NSitBuMe_2)_2) have been found to be reactive toward aromatic N-heterocycles such as 1-methylimidazole and pyridines. These reactions were investigated experimentally and computationally. An initial C−H activation event is followed by a coupling reaction to form biheterocyclic complexes, in which one of the rings is dearomatized. In the case of 1-methylimidazole, the biheterocyclic compound could not be isolated and further led to an imidazole ring-opened product; in the case of pyridines, it transformed into an isomer with extended conjugation of double bonds. Mechanisms for both reactions are proposed on the basis of experimental and computational results. DFT calculations were also used to show that an energetically accessible pathway for the ring-opening of pyridines exists

Flavour from partially resolved singularities

In this letter we study topological open string field theory on D--branes in a IIB background given by non compact CY geometries ${\cal O}(n)\oplus{\cal O}(-2-n)$ on $\P1$ with a singular point at which an extra fiber sits. We wrap $N$ D5-branes on $\P1$ and $M$ effective D3-branes at singular points, which are actually D5--branes wrapped on a shrinking cycle. We calculate the holomorphic Chern-Simons partition function for the above models in a deformed complex structure and find that it reduces to multi--matrix models with flavour. These are the matrix models whose resolvents have been shown to satisfy the generalized Konishi anomaly equations with flavour. In the $n=0$ case, corresponding to a partial resolution of the $A_2$ singularity, the quantum superpotential in the ${\cal N}=1$ unitary SYM with one adjoint and $M$ fundamentals is obtained. The $n=1$ case is also studied and shown to give rise to two--matrix models which for a particular set of couplings can be exactly solved. We explicitly show how to solve such a class of models by a quantum equation of motion technique

The Vector Analyzing Power in Elastic Electron-Proton Scattering

We compute the vector analyzing power (VAP) for the elastic scattering of transversely polarized electrons from protons at low energies using an effective theory of electrons, protons, and photons. We study all contributions through second order in $E/M$, where $E$ and $M$ are the electron energy and nucleon mass, respectively. The leading order VAP arises from the imaginary part of the interference of one- and two-photon exchange amplitudes. Sub-leading contributions are generated by the nucleon magnetic moment and charge radius as well as recoil corrections to the leading-order amplitude. Working to ${\cal O}(E/M)^2$, we obtain a prediction for $A_n$ that is free of unknown parameters and that agrees with the recent measurement of the VAP in backward angle $ep$ scattering.Comment: 24 pages, 11 figures. Typos fixe