Proazaphosphatranes: versatile molecules with applications in fuel cell technology, biodiesel production and important organic transformations

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Wadhwa, Kuldeep
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John G. Verkade
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The Department of Chemistry seeks to provide students with a foundation in the fundamentals and application of chemical theories and processes of the lab. Thus prepared they me pursue careers as teachers, industry supervisors, or research chemists in a variety of domains (governmental, academic, etc).

The Department of Chemistry was founded in 1880.

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In recent years proazaphosphatranes of type P(RNCH2CH2)3N have proven their synthetic utility as catalysts and as stoichiometric bases in a variety of organic transformations. Several reports from our group appeared in which the use of proazaphosphatranes for the activation of the silicon to synthesize useful organic intermediates. Herein we report the use of proazaphosphatranes to synthesize various useful small organic molecules by the activation of Si-O and Si-C bonds, along with efforts to gain evidence for silicon group activation. We previously demonstrated that a phosphatranium cation for which the counter anion is nitrate, is an excellent catalyst for aza- and thia-Michael reactions. Evidence was presented that such a nitrate salt in which the cation was bound to a solid support was superior to a commercially available nitrate anion exchange resin. These results prompted us to chemically bind phosphatranium salts to Nafiony membrane supports to function as nitrate and hydroxide ion conducting membranes for fuel cell applications. Here we report the synthesis of a novel anion exchange fuel cell membrane by chemically attaching proazaphosphatranium and phosphatranium cations under microwave conditions to the sulfonic groups of Nafion-Fy and the use of solid-state NMR techniques to determine the structure and composition of this anion exchange membrane. A thermally and air stable derivative of a proazaphosphatrane i.e., a benzyl azidoproazaphosphatrane, was discovered in our laboratory which was shown to be an excellent catalyst for biodiesel synthesis via the transesterification of soybean oil and for other Lewis base- catalyzed important organic transformations. However, the heterogeneous analog i.e., a Merrifield resin-bound azidoproazaphosphatrane, was found to be deactivated after 11 cycles for the transesterification of soybean oil. We report here an attempted synthesis of a Teflony- and Nafiony-bound azidoproazaphosphatrane. Such a solid support would enable our catalyst system to be stable to elevated temperatures and hydrolytic conditions. Moreover, high recyclability and resistance to plugging of the polymer pores by organic impurities would also be a very beneficial potential outcome.

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