Two molar amounts of arynes were found to couple with nitriles via carbon-carbon sigma-bond cleavage, assembling diverse diarylmethane skeletons in a straightforward manner.

DFT calculations (B3LYP/LANL2DZ/6-31 G*) were used to investigate the ways in which 1-methyl-4-phenyl-1-azabuta-1,3-diene and 4-phenyl-1-oxabuta-1,3-diene bind to a Fe(CO)(4) moiety. As possible coordination modes, eta(2)-coordination across the C=C or C=N/C=O bond, sigma-coordination to the lone pair of the heteroatom, or eta(3)-coordination through the C=C-C or the N=C-C/O=C-C moiety were con...

The observed V3 torsional barriers measured by microwave spectroscopy for nine methyl groups attached alpha to peptide bond linkages in five gas-phase biomimetics have been found to differ considerably from one molecule to the next and even depend on the position of substitution, being sensitive to structural changes at the other end of the peptide bond. In the search for an explanation for the...

The fragmentation of positively charged gas-phase samples of peptides is used to infer the primary structure of such molecules. In electron capture dissociation (ECD) experiments, very low-energy electrons attach to the sample and rupture bonds to effect the fragmentation. It turns out that ECD fragmentation tends to produce cleavage of very specific types of bonds. In earlier works by this gro...

We write the thermodynamic Bethe ansatz for the massive OSp(2|2) Gross Neveu and sigma models. We find evidence that the GN S matrix proposed by Bassi and Leclair [12] is the correct one. We determine features of the sigma model S matrix, which seem highly unconventional; we conjecture in particular a relation between this sigma model and the complex sine-Gordon model at a particular value of t...

Density functional theory has been used to assess the role of the bimetallic core in supporting reductive cleavage of the N=N double bond in [Cp2Mo2(mu-SMe)3(mu-eta1:eta1-HN=NPh)]+. The HOMO of the complex, the Mo-Mo delta orbital, plays a key role as a source of high-energy electrons, available for transfer into the vacant orbitals of the N=N unit. As a result, the metal centres cycle between ...

We study the distribution P(sigma) of the equivalent conductance sigma for Erdös-Rényi (ER) and scale-free (SF) weighted resistor networks with N nodes. Each link has conductance g triple bond e-ax, where x is a random number taken from a uniform distribution between 0 and 1 and the parameter a represents the strength of the disorder. We provide an iterative fast algorithm to obtain P(sigma) an...

We present the first derivation of explicit analytic expressions for the environmental dependence of the sigma, pi, and delta bond integrals within the orthogonal two-center tight-binding approximation by using the recently developed bond-order potential theory to invert the nonorthogonality matrix. We illustrate the power of this new formalism by showing that it not only captures the transfera...

The two-electron reduction of strained pyrenes ([7](2,7)pyrenophanes) with lithium metal leads to the formation of a new sigma-bond as a means to "escape" strained antiaromaticity.