Solvent Effects on Heterogeneous Rate Constants for Indium Mediated Allylations.

Indium mediated allylation is a highly selective tool for synthetic chemists to create carbon-carbon bonds, but the first step, heterogeneous reaction of allyl halides at solid indium surfaces, is still poorly understood. For example, the nature of the solvent dramatically affects the rate of reaction, but solvent choice is often based on empirical experiments. Fundamental kinetic studies are the best way to study this effect, but the determination of heterogeneous rate constants is challenging. In an effort to better understand solvent effects, we use optical microscopy to determine heterogeneous rate constants for IMA in aqueous acetonitrile, methanol, ethanol, and 2-propanol. We fit the reaction rate data over a range of mass transport rates using only two adjustable parameters, the heterogeneous rate constant and the mass transport rate. The results emphasize the critical importance of water in determining the rate of reaction. Surprisingly, the polarity of the organic solvent in the mix does not have a major effect on the rate. It is hypothesized that the oxygen atom in water and alcohols is an especially effective Lewis base to stabilize the transition state and the organoindium intermediates, similar to the importance of the oxygen in ethers for the formation of Grignard reagents. This study again demonstrates the power of microscopy for the study of heterogeneous reactions.

Heterogeneous rate constants for indium mediated allylations: cinnamyl chloride in ethanol/water mixtures.

Indium mediated allylation (IMA) offers a powerful tool to synthetic chemists for creating carbon-carbon bonds. However, its rate limiting step, the heterogeneous reaction of allyl halides at solid indium surfaces, is still poorly understood. For example, solvent effects, especially the presence of water, on IMA are dramatic. We report for the first time rate constants for the heterogeneous rate limiting step of IMA. The rate constant for reaction of cinnamyl chloride on indium decreases from 5.5 × 10(-4) cm/s in 80% ethanol/20% water to 1 × 10(-4) cm/s in 99.8% ethanol/0.2% water. In addition, the percent water has a dramatic effect on induction time. This study further establishes photomicroscopy as a powerful tool for the determination of heterogeneous rate constants.

Measurement of heterogeneous reaction rates: three strategies for controlling mass transport and their application to indium-mediated allylations.

We describe three new strategies for determining heterogeneous reaction rates using photomicroscopy to measure the rate of retreat of metal surfaces: (i) spheres in a stirred solution, (ii) microscopic powder in an unstirred solution, and (iii) spheres on a rotating shaft. The strategies are applied to indium-mediated allylation (IMA), which is a powerful tool for synthetic chemists because of its stereoselectivity, broad applicability, and high yields. The rate-limiting step of IMA, reaction of allyl halides at indium metal surfaces, is shown to be fast, with a minimum value of the heterogeneous rate constant of 1 × 10(-2) cm/s, an order of magnitude faster than the previously determined minimum value. The strategies described here can be applied to any reaction in which the surface is retreating or advancing, thereby broadening the applicability of photomicroscopy to measuring heterogeneous reaction kinetics.

Determining proton diffusion in polymer films by lifetimes of luminescent complexes measured in the frequency domain.

Polymer-supported luminescent metal complexes represent an important class of oxygen, pH, and ion sensors. The diffusion properties of the analyte into the sensing film are important for rational sensor and support design and development. We describe a technique using lifetime measurements in the frequency domain for determining the diffusion coefficient of hydrochloric acid through various polymeric pH sensor films. Two types of polymers are doped with [Ru(4,7-diphenyl-1,10-phenanthroline)2(4,4'-dicarboxy-2,2'-bipyridine)]Cl2. We monitor the phase shift of luminescence (from which we calculate the apparent lifetime, tau(app)) versus time after applying a step increase in the aqueous HCl concentration at the surfaces of the film. We model the decrease in tau(app) as a function of time using the diffusion coefficient of HCl in the polymer as the only adjustable parameter. The model accurately predicts the lifetime versus time curves, and the resulting diffusion coefficients are highly dependent on the polymer. Relative to bulk water, diffusion of protons within very hydrophilic hydrated D4 polymer (a polyethylene oxide cross-linked siloxane ring polymer) films is hindered approximately 4-fold, while within a more hydrophobic sol gel it is hindered by over 1 order of magnitude. The methodology is adaptable for measuring diffusion coefficients of a variety of analytes in different sensor films as long as the bound and unbound forms luminescence and the excited states have different lifetimes.

Measurement of heterogeneous reaction rates during indium-mediated allylation.

Indium-mediated allylation provides remarkable stereo- and regioselectivity, and it proceeds easily and in high yield in aqueous solutions. In spite of its widespread use, there have been few fundamental studies of this reaction. We have developed a photomicrographic technique for measuring rates of reaction of allyl halides at indium surfaces, and we describe the mathematical model for discriminating between diffusion and kinetic control. The measurements demonstrate that this reaction is diffusion controlled, and the minimum value of the heterogeneous rate constant is 1 x 10(-3) cm s(-1). These results broaden the applicability of photomicroscopy for measuring heterogeneous rates of reactions that result in consumption of solid metals.

Determining oxygen diffusion coefficients in polymer films by lifetimes of luminescent complexes measured in the frequency domain.

Polymer films doped with luminescent ruthenium complexes are proving to be important oxygen sensors. We describe a technique using lifetime measurements in the frequency domain for determining the diffusion coefficient of oxygen through various polymer supports. These fundamental measurements will allow for more rational design of improved sensors. Three types of polymers were doped with [Ru(4,7-diphenyl-1,10-phenanthroline)3]Cl2. We monitored the luminescence versus time after applying a step increase in the oxygen pressure at the surface of the film. We modeled the decrease in apparent lifetime as a function of time using the diffusion coefficient of oxygen in the polymer as the only adjustable parameter. The model accurately predicted the lifetime versus time curves, and diffusion coefficients agreed well with those obtained from intensity measurements. The advantages and disadvantages of the lifetime technique to those used earlier are discussed.