Metal Identity Effects in the Pincer Complex-Catalyzed Dehydrogenative Coupling of Formamides with Alcohols to Form CarbamatesClick to copy article linkArticle link copied!
- Abebu A. KassieAbebu A. KassieDepartment of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109, United StatesMore by Abebu A. Kassie
- Ila Y. Castro De la TorreIla Y. Castro De la TorreDepartment of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109, United StatesMore by Ila Y. Castro De la Torre
- Matthew S. Remy
- Sukrit MukhopadhyaySukrit MukhopadhyayCorporate R&D, Dow, Midland, Michigan 48667, United StatesMore by Sukrit Mukhopadhyay
- Jeff KampfJeff KampfDepartment of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109, United StatesMore by Jeff Kampf
- Fengrui QuFengrui QuDepartment of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109, United StatesMore by Fengrui Qu
- Melanie S. Sanford*Melanie S. Sanford*Email: [email protected]Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109, United StatesMore by Melanie S. Sanford
Abstract
This manuscript describes the impact of metal (ruthenium versus iron versus manganese) on the PNP pincer complex-catalyzed dehydrogenative coupling of formamides with alcohols to yield carbamates. Studies are conducted to compare the structure and reactivity of key organometallic intermediates as a function of metal. These reveal that all three pincer catalysts undergo fast reaction with isocyanates (the initial organic products of formamide dehydrogenation) to form off-cycle metallacyclic species. However, the structures and reactivities of these intermediates vary as a function of metal. The N-bound isomer of the metallacycle is formed with Fe (literature) and Ru (this work), while both O-bound (kinetic) and N-bound (thermodynamic) metallacycles are observed with Mn (this work). At 100 °C, the O-bound Mn cycloadduct reacts rapidly with cyclohexanol to release the pincer catalyst along with the corresponding carbamate. In contrast, all three of the N-bound metallacycles show dramatically lower reactivity toward catalyst regeneration under analogous conditions. The reactivity of the pincer complexes toward formamide dehydrogenation also varies as a function of metal, with Ru and Fe ≫ Mn at 100 °C. Overall, the Mn pincer complex is an effective catalyst for the conversion of a variety of formamides and alcohols to carbamates at 150 °C with catalyst loadings as low as 1 mol %. The catalyst performance and substrate scope are comparable to those of the Fe analogue.
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