Electronic communication in oligometallic complexes with ferrocene-based tris(1-pyrazolyl)borate ligands

Ferrocene-based tris(1-pyrazolyl)borate ligands 1R-Li and 1R-Tl have been synthesized and used to generate a variety of heterotrinuclear transition metal complexes, 3R-M [R = H, SiMe(3), cyclohexyl, (cyclohexyl)methyl, phenyl; M(II) = Mn, Fe, Co, Ni, Cu, Zn]. The poor solubility of 3H-M is greatly enhanced by the introduction of large organic substituents into the 4-positions of all pyrazolyl rings. The unsubstituted ligand 1H-Li and the trinuclear complex 3Cym-Cu [Cym = (cyclohexyl)methyl] have been investigated by X-ray crystallography. 1H-Li, which represents the first example of a structurally characterized lithium tris(1-pyrazolyl)borate, forms centrosymmetric dimers in the solid state. A severe Jahn-Teller distortion was observed for the (Bpz(3))(2)Cu fragment in 3Cym-Cu. Compared to the parent compounds [(HBpz(3))(2)M], the presence of uncharged ferrocenyl substituents in 3R-M tends to shift the M(2+)/M(3+) redox potential to significantly more cathodic values. The opposite is true if the ferrocenyl fragments are in their cationic state, which results in an anodic shift of the M(2+)/M(3+) transition. Most interestingly, the two ferrocenyl fragments in 3R-Cu appear to be electronically communicating.     

Radical cation ester cleavage in solution: mechanism of the mesolytic O-CO bond scission

A wide range of enol carbonate, carbamate, and ester radical cations is characterized in solution by cyclic voltammetry and EPR spectroscopy. Preparative transformations using one-electron oxidants or anodic oxidation yield benzofurans after O-CO bond cleavage. Mechanistic investigations and direct detection of radical intermediates reveal that all enol radical cations undergo exclusively O-CO bond cleavage to provide alpha-carbonyl cations and acyl (or alternatively, alkoxyacyl and aminoacyl) radicals, respectively. The kinetics of the mesolytic fragmentation and the influence of nucleophilic additives have been determined using fast-scan cyclic voltammetry.     

Fokker–Planck Equation,Molecular Friction,and Molecular Dynamics for Brownian Particle Transport near External Solid Surfaces

The Fokker–Planck (FP) equation describing the dynamics of a single Brownian particle near a fixed external surface is derived using the multiple-time-scales perturbation method, previously used by Cukier and Deutch and Nienhuis in the absence of any external surfaces, and Piasecki et al. for two Brownian spheres in a hard fluid. The FP equation includes an explicit expression for the (time-independent) particle friction tensor in terms of the force autocorrelation function and equilibrium average force on the particle by the surrounding fluid and in the presence of a fixed external surface, such as an adsorbate. The scaling and perturbation analysis given here also shows that the force autocorrelation function must decay rapidly on the zeroth-order time scale ₀, which physically requires N _Kn1, where N _Kn is the Knudsen number (ratio of the length scale for fluid intermolecular interactions to the Brownian particle length scale). This restricts the theory given here to liquid systems where N _Kn1. For a specified particle configuration with respect to the external surface, equilibrium canonical molecular dynamics (MD) calculations are conducted, as shown here, in order to obtain numerical values of the friction tensor from the force autocorrelation expression. Molecular dynamics computations of the friction tensor for a single spherical particle in the absence of a fixed external surface are shown to recover Stokes' law for various types of fluid molecule–particle interaction potentials. Analytical studies of the static force correlation function also demonstrate the remarkable principle of force-time parity whereby the particle friction coefficient is nearly independent of the fluid molecule–particle interaction potential. Molecular dynamics computations of the friction tensor for a single spherical particle near a fixed external spherical surface (adsorbate) demonstrate a breakdown in continuum hydrodynamic results at close particle–surface separation distances on the order of several molecular diameters.     

Infrarot-Analyse von Arzneimitteln

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Die Bestimmung von Benzolderivaten

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