The aldehyde water shift (AWS) reaction is a fundamentally new organometallic transformation that utilizes water as an oxidant to convert aldehydes to carboxylic acids. The genesis of this project was a report of unusual side products by Stanley and coworkers during the catalytic hydroformylation of olefins.<i> Intrigued by these reports, researchers in the Center for Enabling New Technologies through Catalysis (CENTC) – an NSF Center for Chemical Innovation – investigated the AWS reaction via integrating experiment and theory to develop more active and selective catalysts. From the perspective of catalyst modeling, the study of AWS brought with it particular challenges given the dearth of relevant experimental mechanistic precedents to calibrate the theory. While a complete mechanistic deconvolution of AWS remains elusive, our research has revealed interesting insight into this unusual reaction and raised some interesting mechanistic hypotheses. For example, the activity and selectivity of AWS catalysts is related to the hydricity of a metal-hydride intermediate, which spurred collaborative efforts to determine this important thermodynamic parameter in aqueous media in conjunction with experimental researchers in CENTC. Furthermore, CENTC researchers have developed a heterogeneous variant of AWS using cascade concepts to design these catalysts, in particular building in sites for water decomposition and aldehyde partial oxidation (with the O from water).<br/><br/>

Aldehyde water shift reaction: Integrating theory and experiment to deconvolute a catalytic transformation

254th National Meeting (2017)

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