3 research outputs found
Film-Thickness, Pressure-Gradient, and Turbulent Velocity Profiles in Annular Dispersed Flows
Quinobis(imidazolylidene): Synthesis and Study of an Electron-Configurable Bis(N-Heterocyclic Carbene) and Its Bimetallic Complexes
Reaction of bromanil with N,N'-dimesitylformamidine followed by deprotonation with NaN(SiMe3)(2) afforded 1,1',3,3'-tetramesitylquinobis(imidazolylidene) (1), a bis(N-heterocyclic carbene) (NHC) with two NHC moieties connected by a redox active p-quinone residue, in 72% yield of isolated compound. Bimetallic complexes of I were prepared by coupling to FcN(3) (2) or FcNCS (3; Fc = ferrocenyl) or coordination to [M(cod)Cl] (4a or 4b, where M = Rh or It, respectively; cod = 1,5-cyclooctadiene). Treatment of 4a and 4b with excess CO(g) afforded the corresponding [M(CO)(2)Cl] complexes 5a and 5b, respectively. Analysis of 2-5 by NMR spectroscopy and X-ray diffraction indicated that the electron-deficient quinone did not significantly affect the inherent spectral properties or coordination chemistry of the flanking imidazolylidene units, as compared to analogous NHCs. Infrared spectroscopy and cyclic voltammetry revealed that decreasing the electron density at MLn afforded an increase in the stretching energy and a decrease in the reduction potential of the quinone, indicative of metal-quinone electronic interaction. Differential pulse voltammetry and chronoamperometry of the metal-centered oxidations in 2-4 revealed two single, one-electron peaks. Thus, the metal atoms bound to 1 are oxidized at indistinguishable potentials and do not appear electronically coupled. However, the metal-quinone interaction was used to increase the electron density at coordinated metal atoms. Infrared spectroelectrochemistry revealed that the average nu(CO) values for 5a and 5b decreased by 14 and 15 cm(-1), respectively, upon reduction of the quinone embedded within 1. These shifts correspond to 10 and 12 cm(-1) decreases in the Tolman electronic parameter of this ditopic ligand